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US4786749A - Carboxyl-terminated lactone acrylates - Google Patents

Carboxyl-terminated lactone acrylates Download PDF

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Publication number
US4786749A
US4786749A US06/831,777 US83177786A US4786749A US 4786749 A US4786749 A US 4786749A US 83177786 A US83177786 A US 83177786A US 4786749 A US4786749 A US 4786749A
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Prior art keywords
acrylate
anhydride
acid
caprolactone
product
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US06/831,777
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Joseph V. Koleske
George T. Kwiatkowski
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Union Carbide Corp
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Union Carbide Corp
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Priority to US06/831,777 priority Critical patent/US4786749A/en
Assigned to UNION CARBIDE CORPORATION, A CORP OF NY reassignment UNION CARBIDE CORPORATION, A CORP OF NY ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: KWIATKOWSKI, GEORGE T., KOLESKE, JOSEPH V.
Priority to CA000530088A priority patent/CA1318326C/en
Priority to DE3789464T priority patent/DE3789464T2/en
Priority to DK086987A priority patent/DK86987A/en
Priority to BR8700817A priority patent/BR8700817A/en
Priority to NO870685A priority patent/NO870685L/en
Priority to EP87102441A priority patent/EP0235704B1/en
Priority to AU69110/87A priority patent/AU6911087A/en
Priority to JP62036003A priority patent/JP2527952B2/en
Priority to KR870001421A priority patent/KR870007961A/en
Priority to AT87102441T priority patent/ATE103583T1/en
Publication of US4786749A publication Critical patent/US4786749A/en
Application granted granted Critical
Priority to SG105594A priority patent/SG105594G/en
Priority to JP6271811A priority patent/JP2617429B2/en
Priority to JP6271810A priority patent/JP2811542B2/en
Priority to JP8221892A priority patent/JP2893656B2/en
Priority to JP10032393A priority patent/JP2954917B2/en
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F20/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety

Definitions

  • This invention pertains to lactone acrylates and more particularly to carboxyl-terminated lactone acrylates, their synthesis, and their polymerization products.
  • R is H, methyl or ethyl
  • R' is an alkylene radical having 2 to about 12 carbons
  • R" is an alkylene radical having about 1 to about 10 carbons
  • R'" is a divalent radical having 2 to about 20, preferably 2 to about 12, carbons
  • m is an integer having a value of 1 to about 20, preferably 1 to about 10, most preferably 1 to 5
  • z is an integer having a value of 1 to about 4, preferably 1 to 2.
  • R and R 1 are divalent radicals
  • R 2 is either hydrogen or methyl
  • each of R 3 and R 4 (which can be the same or different) is hydrogen, phenyl, or lower alkyl having 1 to about 6 carbon atoms
  • x is an integer having a value of up to about 10
  • y is an integer having a value up to about 20.
  • Hydroxyalkyl acrylates useful for affording the starting lactone acrylate include:
  • lactones are represented by the formula: ##STR3## wherein each of R 3 and R 4 is hydrogen, phenyl, or lower alkyl having 1 to about 5 carbon atoms and n is 0 to about 9.
  • the preferred lactone is epsilon-caprolactone, although delta-valerolactone, delta-butyrolactone, beta-propiolactone zeta-enantholactone, and eta-caprylolactone can also be used, as well as methyl epsilon-caprolactone, dimethyl epsilon-caprolactone, epsilon-phenyl-alpha-methyl-epsilon caprolactone, and the like, as well as mixtures of such lactones.
  • lactone acrylate used in this invention is that having the average formula
  • the lactone acrylate and anhydride or carboxylic acid compound are combined and allowed to react at temperatures of from room temperature to about 180° C. for periods of time ranging from less than an hour to several days, with the length of reaction time depending on the temperature employed. Both time and temperature will depend on the particular reactants used.
  • the preferred reaction temperatures are from about 40° C. to 160° C. for less than an hour to about twenty-four hours, and the most preferred reaction temperatures are from about 60° C. to 140° C. for less than an hour to about eight hours.
  • the reaction is preferably carried out in an oxygen-containing atmosphere which may be produced by blanketing the reactants with air, sparging the reactants with air, or by any other means that will introduce oxygen and inhibit reaction of the acrylate functionality.
  • a catalyst to promote the reaction and minimize the reaction time.
  • Suitable catalysts are alkaline compounds such as tetramethylammonium bromide, trimethylbenzyl ammonium hydroxide, trimethylbenzylammonium ethoxide, trimethylbenzyl ammonium bromide and other quaternary ammonium compounds. It is desirable to add an inhibitor or free radical stabilizer to the reacting system to prevent gelation when oxygen alone is not sufficient for this purpose.
  • a variety of quinones such as hydroquinone monomethyl ether, hydroquinone, alkyl- and aryl-substituted hydroquinone, p-methyoxyphenol, and so on, can be used as free radical stabilizers. These inhibitors can be used in concentrations of from about 100 to 2000 ppm, preferably from 200 to 700 ppm, of the reactants. In many instances, the starting lactone acrylate will contain one or more of these inhibitors. If desired, an inert solvent or a reactive solvent can be used in the preparation of the carboxyl-terminated lactone acrylates.
  • Inert solvents are such materials as toluene, 1,1,1-trichloroethane, ethoxyethanol acetate, and the like, and reactive solvents are various compounds such as 2-ethyl hexyl acrylate, 1,6-hexanediol diacrylate, trimethylolpropanetriacrylate, and the like.
  • the amount of polycarboxylic acid anhydride to be reacted with the caprolactone acrylate can be an amount sufficient to react with all of the hydroxyl groups; however, it may be desirable to use an amount of anhydride which is insufficient to react with all of the hydroxyl groups present in the caprolactone acrylate.
  • This amount will vary and can be from about 0.1 to one anhydride equivalent or anhydride moiety for each hydroxyl equivalent or group present in the caprolactone acrylate, preferably from about 0.4 to one anhydride equivalent or anhydride moiety for each hydroxyl group present in the caprolactone acrylate, and more preferably from about 0.6 to one anhydride equivalent or anhydride moiety for each hydroxyl group. In a most preferred instance, one anhydride equivalent or anhydride moiety is charged for each hydroxyl equivalent or group initially present in the reaction mixture.
  • lactone acrylates which are the reaction products of a lactone or mixture of lactones such as epsilon-caprolactone or a mixture of epsilon-caprolactone and epsilon-methyl-epsilon-caprolactone and a hydroxyalkyl acrylate such as hydroxyethyl acrylate or hydroxyethyl methacrylate, with an intramolecular polycarboxylic acid anhydride such as maleic anhydride.
  • lactone acrylates which are the reaction products of a lactone or mixture of lactones such as epsilon-caprolactone or a mixture of epsilon-caprolactone and epsilon-methyl-epsilon-caprolactone and a hydroxyalkyl acrylate such as hydroxyethyl acrylate or hydroxyethyl methacrylate.
  • carboxylic acids can be reacted with the caprolactone acrylate via a condensation mechanism to yield monofunctional or polyfunctional compounds or mixtures thereof.
  • These polyfunctional compounds can have single or multiple acrylate functionality and/or single or multiple carboxyl functionality.
  • the resulting compound of this invention can have mono or multiple acrylate functionality and/or mono or multicarboxyl functionality.
  • monofunctional carboxylic acids or anhydrides such as acetic anhydride
  • the product will be an ester- or substituted ester-terminated molecule.
  • the preferred reactant is an anhydride, which provides for more facile reaction conditions.
  • This compound and the other derivatives or adducts contemplated can be used in a variety of ways.
  • they can be used as radiation-curable monomers that will cure alone or in combination with other acrylates, diacrylates, triacrylates, multifunctional acrylates, vinyls, and the like, with variousforms of radiation, such as ultraviolet light, electron beam radiation, gamma radiation, X-rays, etc.
  • radiation-curable monomers that will cure alone or in combination with other acrylates, diacrylates, triacrylates, multifunctional acrylates, vinyls, and the like, with variousforms of radiation, such as ultraviolet light, electron beam radiation, gamma radiation, X-rays, etc.
  • a photoinitiator that generates free radicals
  • benzophenone benzoin ethers
  • diethoxyacetophenone diethoxyacetophenone
  • the compounds of the invention can be cured alone or in combination with other reactants by thermal means.
  • a peroxide may be included in the formulated system.
  • driers can be of various types, such as cobalt naphthenate, manganese naphthenate, iron hexoate, calcium octoate, and the like.
  • the compounds and/or polymers of this invention are useful in a variety of coating, ink, adhesive, and sealant applications, as dispersants, as water dispersible/soluble materials, as hardeners, as tougheners, etc.
  • the trifunctional molecules prepared from maleic anhydride and lactone acrylate monomers can be used in a wide variety of ways since they contain acrylate, maleate, and carboxyl functionality.
  • high functionality unsaturated molecules can be prepared from polyfunctional anhydrides and the lactone acrylates.
  • the molecules of this invention that contain maleic anhydride residues can also be combined with styrene to form useful radiation-cure coatings.
  • the compounds of this invention can be used as the only thickener or in combination with other thickeners, such as carboxyl-terminated caprolactone polyols, carboxyl-containing vinyl copolymers, and the like.
  • two molecules of lactone acrylate can be used in the above-depicted reaction of a lactone acrylate with an anhydride, with the second molecule reacting with the carboxyl group of the indicated reaction product via a condensation mechanism to yield a diacrylate.
  • This can be used in various ways, such as a cross-linking agent for coatings and so on.
  • the carboxyl-terminated lactone acrylates can be reacted with a variety of mono- or polyhydric alcohols to form the corresponding esters, which are useful as flexibilizers for radiation-cure formulations, in other uses that require acrylates, such as oligomers and polymers, and as high-boiling solvents.
  • alcohols can be used, as for example, methanol, which would yield the methyl ester of the lactone acrylate, ethanol, which would yield the ethyl ester of the lactone acrylate, propanol, iso-propanol, n-butanol, s-butanol, i-butanol, t-butanol, and so on.
  • Useful polyhydric alcohols would include glucose, sucrose, glycerol, sorbitol, inositol, and so on.
  • the lactone acrylate can be reacted with acetic anhydride to form the methyl ester of the lactone acrylate or it can be reacted with various monocarboxylic acids to form a variety of esters.
  • esters are not acid-terminated, they are useful as acrylates in the preparation of polymers or oligomers than may be crosslinked or that can be used in radiation curable systems. In general, such novel compounds are useful as flexibilizers.
  • useful products can have from one to twenty or more caprolactone units per acrylate group, or can be a mixture of compounds that contain from one to about twenty or more lactone units.
  • these units could be other lactones such as beta-propiolactone, delta-valerolactone, delta-butyrolactone, zeta-enantholactone, eta-caprylolactone, and so on, or substituted lactones such as 6-methyl-epsilon-caprolactone, 3-methyl-epsilon-caprolactone, 5-methyl-epsilon-caprolactone, 5-phenyl-epsilon caprolactone, 4-methyl-delta-valerolactone, 3,5-dimethyl-epsilon caprolactone, and so on, or copolymers of such lactones, such as a copolymer of epsilon-caprolactone and epsilon-methyl-epsilon caprolactone, of epsilon-caprolactone and eta-caprylolactone, of delta-valerolactone and epsilon-methyl-eps, and
  • lactones and oxides such as ethylene oxide, propylene oxide, butylene oxide, and so on
  • the lactone acrylate can be prepared from one or more lactones alone or in combination with one or more of the described oxides.
  • the lactone acrylate can be prepared by reacting a hydroxyalkyl acrylate and a mixture of caprolactone, diacid--such as adipic acid, and diol--such as 1,6-hexane diol.
  • diols are also useful in place of, or in addition to, diols, such as triols, tetrols, and so on.
  • one or more oxides can be included in the reaction mixture.
  • Further types of lactone acrylate will be those described above that have been end-capped with one or more moles of an alkylene oxide or of a tetrahydrofuran.
  • n has a value of one to about ten or more.
  • This oxide-capped molecule can be reacted with an anhydride to produce the molecules of this invention. If desired, before reacting the oxide-capped caprolactone acrylate with an anhydride, it could be further reacted with a lactone to form a block copolymer with alternating blocks that are the same or different in composition. Finally, the copolymeric acrylate would be reacted with an anhydride to produce the molecules of this invention.
  • lactones Although a variety of lactones can be used, the preferred lactones to be used in the preparation of the caprolactone acrylates are epsilon-caprolactone and substituted epsilon-caprolactone. The most preferred lactone is epsilon-caprolactone.
  • the hydroxyalkyl acrylates that can be used to produce the lactone acrylate are 2-hydroxyethyl, 2-hydroxypropyl, 2-hydroxybutyl, 3-hydroxypropyl acrylate or methacrylate, diethylene glycol monoacrylate or monomethacrylate, glycerine or trimethylolpropane mono- or diacrylate or mono- or dimethacrylate, pentaerythritol mono-, di-, or triacrylate or mono-, di-, or trimethacrylate, glucose or sorbitol mono-, di-, tri-, tetra-, and penta-acrylate, or mono-, di-, tri-, tetra-, and pentamethacrylate, and the like. If desired, mixtures of one or more of these acrylates can be used in preparing the lactone acrylate of this invention.
  • Cyclic anhydrides of carboxylic acids are preferred for reaction with the lactone acrylates. However, if desired, mono- and polyfunctional carboxylic acids may be used wherein a condensation mechanism is employed. Anhydrides are preferred. Among the various anhydrides that can be used for the practice of this invention are maleic anhydride, succinic anhydride, phthalic anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, glutaric anhydride, cis- and trans-1,2-cyclohexane dicarboxylic anhydride, citraconic anhydride, itaconic anhydride, dodecenyl anhydride, isophthalic anhydride, hexachlorophthalic phthalic anhydride, chlorendic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid dianhydride, naphthoic anhydride, norbornene
  • mixtures of one or more anhydrides and/or carboxylic acids can be used.
  • anhydride can be used per equivalent of hydroxyl and it is preferred to use about 0.4 to about one equivalent of anhydride per equivalent of hydroxyl, and it is preferred to use from 0.6 to one equivalent of anhydride per equivalent of hydroxyl.
  • one anhydride equivalent or anhydride moiety is charged for each hydroxyl equivalent or group initially present in the reaction mixture.
  • Illustrative of the monofunctional carboxylic acid compounds that can be used one can name pentanoic acid, hexanoic acid, octanoic acid, caprylic acid, capric acid, hendecanoic acid, lauric acid, tridecanoic acid, pentadecanoic acid, stearic acid, arachidic acid, behenic acid, benzoic acid, cerotic acid, 2-ethylhexanoic acid, naphthoic acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, oleostearic acid, levulinic acid, ricinoleic acid, cinnamic acid, and the like, and mixtures of such acids.
  • polyfunctional carboxylic acids that can be used, one can mention oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, maleic acid, fumaric acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, tartaric acid, malic acid, mannaric acid, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,4,5,6,7,7-hexachloro-5-norbornene-2,3-dicarboxylic acid, hexahydophthalic acid, galactaric acid, 4,5-cyclohexenedicarboxylic acid, 3,6-methylene- 4-cyclohexene-1,2-dicarboxylic acid, citric acid, and the like, as well as mixtures of these
  • the carboxylic acids can be unsubstituted or they can be substituted with any group which will not significantly interfere with the reaction.
  • suitable substituents are the halogens, nitro, alkoxy, alkyl, keto, and the like.
  • the anhydride-capped lactone acrylates of this invention can be used in many ways. These ways of utilizing the compounds include homopolymerization or copolymerization with a variety of other suitable acrylates, methacrylates, or other ethylenically unsaturated compounds that will undergo copolymerization by radiation reaction techniques.
  • Suitable compounds for copolymerization include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary-butyl, tertiary-butyl, pentyl, neopentyl, isopentyl, hexyl, ethyl-hexyl, dodecyl, glycidyl, hydroxyalkyl, and so on, acrylates and methacrylates, acrylic and methacrylic acid, 2-polystyrylalkylmethacrylates as 2-polystyrylethylmethacrylate (Arco Chemical Co., Chemlink 4500), vinyl compounds such as vinyl acetate, vinyl chloride, styrene, acrylonitrile, methacrylonitrile, and the like, 1,6-hexanediol diacrylate, trimethylolpropane di- and triacrylate and methacrylate, pentaerythrito
  • Pat. No. 3,169,945 are esterified with acrylic or methacrylic acid, alkoxylated derivatives (i.e., end-capped) of the above-described caprolactone polyols that are esterified with acrylic or methacrylic acid, alkylene oxide polyols or monols that have been esterified with acrylic or methacrylic acid, reaction products of alkylene oxides with monols or polyols such as hydroxyalkyl acrylates or trimethylol propane, pentaerythritol, sorbitol, glucose, etc., that have been esterified with acrylic or methacrylic acid, poly(tetramethylene oxide) polyols that have been esterified with acrylic acid or methacrylic acid, epoxy acrylates, urethane acrylates, and the like.
  • alkoxylated derivatives i.e., end-capped
  • photoinitiators can be utilized in the radiation-curing aspect of this invention.
  • the usually used photoinitiators are the type that generate free radicals when exposed to radiation energy. Any of the known photoinitiators can be used.
  • Suitable photoinitiators one can mention 2,2-diethoxyacetophenone, 2- or 3- or 4-bromoacetophenone, 3- or 4-allyl-acetophenone, 2-acetonaphthone, benzaldehyde, benzoin, the alkyl benzoin ethers, benzophenone, benzoquinone, 1-chloroanthraquinone, p-diacetyl-benzene, 9,10-dibromoanthracene, 9,10-dichloroanthracene, 4,4-dichlorobenzophenone, thioxanthone, isopropyl-thioxanthone, methylthioxanthone, a, a, a,-trichloro-para-t-butyl acetophenone, 4-methoxybenzophenone, 3-chloro-8-nonylxanthone, 3-iodo-7-methoxyxanthone,
  • photoactivators can be used in combination with the aforementioned photoinitiators and that synergistic effects are sometimes achieved when such combinations are used.
  • Photoactivators are well known in the art and require no further description to make known what they are and the concentrations at which they are effective.
  • photoactivators methylamine, tributylamine, methyldiethanolamine, 2-aminoethylethanolamine, allylamine, cyclohexylamine, cyclopentadienylamine, diphenylamine, ditolylamine, trixylylamine, tribenzylamine, n-cyclohexylethyleneimine, piperidine, N-methylpiperazine, 2,2-dimethyl-1,3-bis(3-N-morpholinyl)-propionyloxypropane, and the like, or any combination of these.
  • the formulations of this invention can be cured by ionizing or non-ionizing radiation means including, but not limited to, ultraviolet light, gamma radiation, and electron beam radiation. These curing methods and the equipment that can be used for them are well known to those skilled in the art.
  • ionizing or non-ionizing radiation means including, but not limited to, ultraviolet light, gamma radiation, and electron beam radiation. These curing methods and the equipment that can be used for them are well known to those skilled in the art.
  • Suitable sources of radiation include mercury, xenon, carbon arc lamps, sunlight, radioactive sources, etc.
  • Exposures may be from less than about 1 second to 10 minutes or more, depending upon the amounts of particular polymerizable materials and photoinitiator being utilized and depending upon the radiation source and distance from the source, and the thickness of the coating to be cured.
  • the compositions may also be photopolymerized by exposure to electron beam radiation. Generally speaking the dosage necessary is from less than 1 megarad to 100 megarads or more
  • compositions of this invention may also include one or more thermoplastic resins free from any radiation-curable, unsaturated bond.
  • thermoplastic resins for this purpose are vinyl chloride-vinyl acetate copolymers and other vinyl chloride resins, cellulose nitrate, cellulose acetate and other polyester resins, polyvinyl alcohol resins, and other cellulose derivatives, thermoplastic polyurethane resins, polyamide resins, polycaprolactone, polyvinylidene chloride, polyacrylates and other acrylic resins.
  • the addition of such a thermoplastic resin is effective in balancing hardness, toughness, flexibility and other properties of the product, as well as providing sag control and viscosity control.
  • many radiation-cure coating systems are solvent-free, they may contain conventional solvents such as cyclohexanone, 1,1,1-trichloroethane, toluene, methyl isobutyl ketone, methyl amyl ketone, ethoxyethyl acetate, methylene chloride, and the like, and mixtures of these solvents, such as, for example a 2:2:1 mixture of methyl isobutyl ketone, toluene and cyclohexane.
  • solvents such as cyclohexanone, 1,1,1-trichloroethane, toluene, methyl isobutyl ketone, methyl amyl ketone, ethoxyethyl acetate, methylene chloride, and the like, and mixtures of these solvents, such as, for example a 2:2:1 mixture of methyl isobutyl ketone, toluene and cyclohexan
  • the coating compositions may preferably include additives in conventional quantities, such as oils, particularly silicone oil, surfactants such as silicone-alkylene oxide copolymers, e.g., L-7604, L-7610, etc., commercially available from Union Carbide Corporation, silicone oil containing aliphatic epoxide groups, fluorocarbon surfactants such as FC-171 commercially available from 3M Commercial Chemicals Division and FC-430 and FC-431 also commercially available from 3M Commercial Chemicals Division, Modaflow commercially available from Monsanto Co., and other similar type compounds that are used to improve the flow and leveling characteristics of coatings.
  • oils particularly silicone oil
  • surfactants such as silicone-alkylene oxide copolymers, e.g., L-7604, L-7610, etc.
  • FC-171 commercially available from 3M Commercial Chemicals Division
  • FC-430 and FC-431 also commercially available from 3M Commercial Chemicals Division
  • Modaflow commercially available from Monsanto Co.
  • the anhydride-capped lactone acrylates of this invention can be combined with the various acrylates mentioned above and the free radical initiators, such as benzoyl peroxide, lauroyl peroxide, and the like, that yield free radicals when heated, to yield highly useful systems. In this case, no photoinitiators are necessary unless one wishes to combine thermal and radiation curing.
  • the free radical initiators such as benzoyl peroxide, lauroyl peroxide, and the like
  • the coating compositions of this invention can contain various additives that are known to those skilled in the art.
  • additives include, pigments, colorants, dyes, defoamers, thickeners, preservatives, mildew inhibitors, anti-sag agents, anti-settling agents, and the like.
  • Forward Impact Resistance a measure of the ability of a cured film coating to resist rupture from a falling weight.
  • a Gardner Impact Tester using an eight-pound dart was used to test film coatings cast and cured on steel panels. The dart was raised to a given height in inches and dropped onto the coating side of the coated steel panel. The inches times pounds, designated inch-pounds, absorbed by the film without rupturing was recorded as the film's forward impact resistance.
  • Pencil Hardness (ASTM D-3363-74): pencil leads of increasing hardness values were forced against the film coating surface in a precisely defined manner until one pencil lead cut through the surface of the film coating. The surface hardness was considered as the hardest pencil grade which just failed to cut through the film coating surface. The pencil leads, in order of softest to hardest, were reported as follows: 6B, 5B, 4B, 3B, 2B, B, HB, F, H, 2H, 3H, 4H, 5H, 6H, 7H, 8H, and 9H.
  • Solvent Resistance a measure of the resistance of the cured film to attack by acetone and was reported as the number of rubs or cycles of acetone-soaked cheesecloth required to remove one-half of a cured film from the test area. This test was performed by stroking the cured film with acetone-soaked cheesecloth until that amount of film coating was removed. The number of cycles required to remove this amount of coating was a measure of the coating's solvent resistance.
  • Reverse Impact Resistance a measure of the ability of a cured film coating to resist rupture from a falling weight.
  • a Gardner Impact Tester using an eight-pound dart was used to test film coatings cast and cured on steel panels. The dart was raised to a given height in inches and dropped onto the uncoated side of the coated steel panel. The inches times pounds, designated inch-pounds, absorbed by the film without rupturing was recorded as the film's reverse impact resistance.
  • Crosshatch Adhesion a lattice pattern with either six or eleven cuts in each direction was made in the coating film to the substrate and pressure-sensitive adhesive tape was applied over the lattice pattern and then removed. The adhesion was evaluated by comparison with descriptions and illustrations, as more fully detailed in ASTM D-3359-78.
  • TONE Monomer M-100 A caprolactone acrylate with an average molecular weight of about 344 and marketed by Union Carbide Corp.
  • Uvithane 893 A urethane acrylate marketed by Thiokol. It is a viscous liquid that has a viscosity of 900 to 2,200 poise at 120° F.
  • Irgacure 184 A free radical-generating photoinitiator that is marketed by Ciba-Geigy. It is stated to be 1-hydrocycyclohexyl phenyl ketone.
  • L-5410 A silicone/alkylene oxide copolymer formerly marketed under that designation by Union Carbide Corporation and now marketed as L-7610 under the SILWET trademark by Union Carbide Corporation.
  • L-7604 and L-7610 are silicone/alkylene oxide copolymers marketed by Union Carbide Corporation.
  • the silicone/alkylene oxide polymers are modified dimethylpolysiloxanes.
  • Esterdiol 204 A methylolated proprionate diol marketed by Union Carbide Corporation.
  • TONE Monomer M-100 One hundred grams of TONE Monomer M-100 were added to a 300 milliliter reaction flask equipped with a stirrer, air inlet and an air outlet, and a thermometer. The M-100 was heated to 110° C. with stirring and an air blanket. When the flask temperature reached 100° C., 24.7 grams of succinic anhydride were added slowly to avoid an exothermic reaction. Addition of the anhydride lowered the temperature about 7° C. The mixture of chemicals was heated for four hours at 117°-120° C. and at 130° C. for one hour. The product was cooled and stored. Analysis indicated that it had an acid number of 124, which would correspond to an average molecular weight of 452, which is quite close to the theoretical molecular weight of 444 for the expected product.
  • Example 2 improves the hardness of the urethane acrylate system (Example 5 vs. Example 3) more than the TONE Monomer M-100 (Example 3 vs. Example 4).
  • the product of Example 2 has effectively not altered the impact resistance of the urethane acrylate whereas the M-100 has caused a marked decrease in impact characteristics.
  • the product of Example 2 achieved both an increase in hardness and in flexibility/impact resistance which is not expected, in that one property usually decreases when the other property increases.
  • the improvement in hardness is apparent when the data of Examples 6 and 7 are compared.
  • the homopolymer of TONE Monomer M-100 is ⁇ 6B in hardness, indicating a very soft coating, whereas the homopolymer of the Example 2 product (Example 7) is 6B in hardness.
  • Example 7 the homopolymer of the Example 7 coating over that of Example 6 coating, to emphasize this difference, the systems of Examples 6 and 7 were subjected to 5 passes under the ultraviolet light source. After this treatment, the coating of Example 6 was still ⁇ 6B in hardness, whereas the coating of Example 7 was 4B in hardness, indicating that there was at least a "three-pencil" hardness difference in the coatings.
  • Example 2 In the same manner as described in Examples 3 to 7, the systems shown in Table II were prepared, cured, and tested. The cured coatings were then evaluated, and they had the properties described below.
  • the purpose in these studies (Ex. 8-15 and 18/19) was to demonstrate that the newly developed product of Example 2 did not decrease hardness of a very hard, radiation-cured system as much as M-100 monomer.
  • the other examples are for the purpose of demonstrating that useful radiation-cured products can be derived from the Example 2 product and a variety of other acrylates.
  • Example 2 is much more effective in maintaining hardness than other additives such as M-100 monomer. This is especially apparent when Examples 10 and 11 are compared with Examples 14 and 15, and when Examples 18 and 19 are compared.
  • Examples 28 and 29 are examples of products prepared from mixtures of an unsaturated anhydride (maleic) and a saturated anhydride (phthalic). Such products can be used to alter the final degree of crosslinking of systems in which they are utilized.
  • the products of Examples 31 and 32 are based on relatively high molecular weight caprolactone acrylates and are for systems in which a high degree of flexibility or other specialized property is desired. These long-chain molecules will provide a plasticizing, softening, or other special effect when used in a variety of systems that can be cured by radiation or heat.
  • Examples 30 and 33 demonstrate that carboxyl-functional methacrylates can be prepared. These methacrylates will usually provide higher hardness along with flexibility than the corresponding acrylates.
  • Examples 36, 37, and 38 indicate that similar properties are obtained when either the phthalate/maleate acrylate mixture or the maleate acrylate alone is used in the particular system investigated. (Results may be different when these products used are in other formulated systems.)
  • Examples 39 and 40 compare the results obtained when a system containing a caprolactone acrylate (Ex. 40) is compared with a mixed phthalate/maleate caprolactone acrylate (Ex. 39). It is readily apparent that a significantly harder coating is obtained with the Ex. 39 system.
  • Table VI describe the combination and radiation (ultraviolet light) cure of carboxyl-terminated caprolactone acrylates prepared in previous examples and other acrylates such as the diacrylate 1,6-hexanediol diacrylate (HD Diacrylate), the triacrylate trimethylolpropane triacrylate (TMP triacrylate), and an epoxy acrylate (Celrad 3700*) or mixtures of such acrylates.
  • the ingredients listed were placed in glass bottles and well mixed. They were warmed to rapidly effect dissolution of the Irgacure 184 photoinitiator.
  • Example 52 0.25 equivalent of M-100 and 0.25 equivalent of methyltetrahydrophthalic anhydride.
  • Example 53 0.25 equivalent of M-100 and 0.25 equivalent of hexahydrophthalic anhydride.
  • Example 54 0.25 equivalent of M-100 and 0.25 equivalent of phthalic anhydride.
  • Example 55 0.375 equivalent of M-100 and 0.125 equivalent of hexahydrophthalic anhydride and 0.25 equivalent of phthalic anhydride.
  • Example 27 describes the blending and radiation curing of mixtures of a carboxyl-terminated caprolactone acrylate and the non-acrylate, ethylenically unsaturated compounds styrene and vinyl pyrrolidone.
  • Example 27 is repeated since it functions as a control with no styrene or vinyl pyrrolidone.
  • Examples 74 and 75 shown in Table X, deal with the preparation of carboxyl-terminated caprolactone acrylates that are prepared from mixtures of anhydrides.
  • the radiation-cure coating systems were formulated from the ingredients shown in Table XI by placing the compounds in amber colored glass bottles, mixing well, and then coating onto Bonderite 37 steel panels with a #20 wire-wound rod. They were then cured with a 300 watt/inch Fusions Systems ultraviolet light source at a rate of 10 fpm.
  • addition of the products of this invention to other acrylates and mixtures of acrylates can improve the impact resistance and improve or not alter the hardness of the starting urethane acrylate.
  • addition of M-100 causes a decrease in coating hardness and less of an improvement in impact resistance.
  • a reactive diluent such as the products of this invention, to the urethane acrylate to decrease viscosity and improve coating application characteristics.
  • the urethane acrylate has a viscosity of 19,500 cp at 20° C. and 3,800 cp at 37.8° C. (manufacturer's specification).
  • This example describes the preparation of a carboxyl-terminated caprolactone acrylate wherein only 90 mole or equivalent percent of the anhydride is used.
  • the example is not meant to limit the amount of anhydride that can be used in the practice of the invention.
  • An epsilon-methyl-epsilon-caprolactone adduct of 2-hydroxyethylacrylate was prepared by placing 128 grams of epsilon-methyl-epsilon caprolactone in a 250 cc, four-necked glass reaction flask equipped with a stirrer, thermometer, an air inlet and an air outlet. This compound was heated to 130° C. and 58 grams of 2-hydroxyethylacrylate, 0.009 gram of stannous octanoate, and 0.06 gram of the monomethylether of hydroquinone were slowly added. After the addition, the temperature dropped to 110° C. The mixture was then heated to 130° C. and held at this temperature for 14 hours. During this reaction time, an air sparge was maintained. After the reaction time had elapsed, the product, an epsilon-methyl-epsilon-caprolactone acrylate, was cooled to room temperature and stored.
  • the cured coatings had the following characteristics: 30 acetone double rubs, 6B pencil hardness, 100% crosshatch adhesion, and 320 in. lbs direct and reverse Gardner impact resistance.
  • a maleic anhydride-capped caprolactone acrylate was prepared from 172.0 grams of M-100 caprolactone acrylate and 49.0 grams of maleic anhydride by using the same equipment, reaction conditions, and reaction times as were used in Example 86.
  • the final product had a viscosity of 402 cp at 25° C. The product was stored for later usage.
  • Eta-caprlolactone (21.0 grams), 2-hydroxyethylacrylate (8.53 grams), stannous octanoate (0.003 gram), and the monomethylether of hydroquinone (0.02 gram) were placed in a 250 cc glass, four-necked reaction flask equipped with a stirrer, thermometer, an air inlet and an air outlet. These ingredients were heated at 130° C. for 8 hours while an air sparge was maintained. The resulting lactone acrylate was cooled to room temperature and stored. The resulting product solidified into a crystalline mass. This product will be referred to as Example 98 Control Product in the following.
  • Example 98 Control Product Twenty grams of Example 98 Control Product and 4.9 grams of maleic anhydride were placed in the reaction flask described in the previous paragraph and heated to 90° C. The ingredients were maintained at this temperature for two hours while maintaining an air sparge. The product was then cooled to room temperature and stored for further use. This product will be referred to as Example 98 Product in the following experimentation.
  • Example 99 94.20 grams of the Example 99 product, a methyl-caprolactone acrylate, and 13.23 grams of maleic anhydride were placed in a 250 cc, glass, four-necked reaction flask equipped with a stirrer, thermometer, an air inlet and an air outlet. These ingredients were heated to 90° C. and held at this temperature for two hours. After this time the carboxyl-terminated caprolactone acrylate was cooled to room temperature and stored for further use. It had a viscosity of 434 cp at 25° C.
  • This example describes the preparation of a copolymeric, epsilon-methyl-epsilon-caprolactone/epsilon-caprolactone, caprolactone acrylate and the corresponding anhydride-capped adduct of said caprolactone acrylate.
  • This example illustrates the preparation of the acetate of TONE Monomer M-100.

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Abstract

Lactone acrylates and organic anhydrides are condensed to form carboxyl-terminated lactone acrylates. These can be homopolymerized or copolymerized with ethylenically unsaturated monomers by means of radiation.

Description

BACKGROUND OF THE INVENTION
This invention pertains to lactone acrylates and more particularly to carboxyl-terminated lactone acrylates, their synthesis, and their polymerization products.
The preparation of certain caprolactone acrylate monomers was disclosed in U.S. Pat. No. 4,504,635 and a particular one is commercially available as TONET Monomer M-100 from Union Carbide Corporation. The following equation describes the preparation of such materials from the reaction of an hydroxyalkyl acrylate and epsilon-caprolactone: ##STR1## wherein R is an alkylene radical having 2 to 12 carbon atoms and p is from 1 to about 20.
SUMMARY OF THE INVENTION
It has now been found that the reaction of a lactone acrylate with an organic anhydride or carboxylic acid compound affords a polymerizable monomeric carboxyl-terminated lactone acrylate having the following general formula:
CH.sub.2 ═CRCO.sub.2 R'--O[COR"--O].sub.m COR'"--[COOH].sub.z
wherein R is H, methyl or ethyl, R' is an alkylene radical having 2 to about 12 carbons, R" is an alkylene radical having about 1 to about 10 carbons, R'" is a divalent radical having 2 to about 20, preferably 2 to about 12, carbons, m is an integer having a value of 1 to about 20, preferably 1 to about 10, most preferably 1 to 5, and z is an integer having a value of 1 to about 4, preferably 1 to 2. The monomeric structure depicted above is obtained by a process in which ester linkages are formed in the presence of other existing ester linkages without deleterious side reactions occurring. In addition, the structures are stable even though carboxylic acid groups are present and such groups are known to have an adverse effect, i.e., as for example cause hydrolysis or metastasis, on lactone-based products such as polyols.
In a preferred reaction scheme, the following equation results: ##STR2## where R and R1 are divalent radicals, R2 is either hydrogen or methyl, each of R3 and R4 (which can be the same or different) is hydrogen, phenyl, or lower alkyl having 1 to about 6 carbon atoms, x is an integer having a value of up to about 10, and y is an integer having a value up to about 20.
Hydroxyalkyl acrylates useful for affording the starting lactone acrylate include:
hydroxyethyl acrylate
hydroxypropyl acrylate
hydroxybutyl acrylate
glycerine mono- or diacrylate
hydroxyethyl methacrylate
hydroxypropyl methacrylate
hydroxyhexyl methacrylate, and the like.
Representative lactones are represented by the formula: ##STR3## wherein each of R3 and R4 is hydrogen, phenyl, or lower alkyl having 1 to about 5 carbon atoms and n is 0 to about 9.
The preferred lactone is epsilon-caprolactone, although delta-valerolactone, delta-butyrolactone, beta-propiolactone zeta-enantholactone, and eta-caprylolactone can also be used, as well as methyl epsilon-caprolactone, dimethyl epsilon-caprolactone, epsilon-phenyl-alpha-methyl-epsilon caprolactone, and the like, as well as mixtures of such lactones.
The most preferred lactone acrylate used in this invention is that having the average formula
CH.sub.2 ═CHCOOCH.sub.2 CH.sub.2 O--[--CO(CH.sub.2).sub.5 --O--].sub.2 H
where 1 mole of hydroxyethyl acrylate combines with 2 moles of epsilon-caprolactone. This product can be prepared as disclosed in U.S. Pat. No. 4,504,635; however, similar reaction products of hydroxyalkyl acrylates and caprolactone prepared with catalysts such as stannous chloride, boron trifluoride, boron trifluoride etherate, dibutyltin oxide, stannous bromide, and the like, can be used.
The general reaction conditions for the conversion of lactone acrylates to carboxyl-terminated derivatives are as follows:
The lactone acrylate and anhydride or carboxylic acid compound are combined and allowed to react at temperatures of from room temperature to about 180° C. for periods of time ranging from less than an hour to several days, with the length of reaction time depending on the temperature employed. Both time and temperature will depend on the particular reactants used. The preferred reaction temperatures are from about 40° C. to 160° C. for less than an hour to about twenty-four hours, and the most preferred reaction temperatures are from about 60° C. to 140° C. for less than an hour to about eight hours. The reaction is preferably carried out in an oxygen-containing atmosphere which may be produced by blanketing the reactants with air, sparging the reactants with air, or by any other means that will introduce oxygen and inhibit reaction of the acrylate functionality. Although the reaction proceeds without an added catalyst, in certain instances it may be desirable to add a catalyst to promote the reaction and minimize the reaction time. Suitable catalysts are alkaline compounds such as tetramethylammonium bromide, trimethylbenzyl ammonium hydroxide, trimethylbenzylammonium ethoxide, trimethylbenzyl ammonium bromide and other quaternary ammonium compounds. It is desirable to add an inhibitor or free radical stabilizer to the reacting system to prevent gelation when oxygen alone is not sufficient for this purpose. A variety of quinones such as hydroquinone monomethyl ether, hydroquinone, alkyl- and aryl-substituted hydroquinone, p-methyoxyphenol, and so on, can be used as free radical stabilizers. These inhibitors can be used in concentrations of from about 100 to 2000 ppm, preferably from 200 to 700 ppm, of the reactants. In many instances, the starting lactone acrylate will contain one or more of these inhibitors. If desired, an inert solvent or a reactive solvent can be used in the preparation of the carboxyl-terminated lactone acrylates. Inert solvents are such materials as toluene, 1,1,1-trichloroethane, ethoxyethanol acetate, and the like, and reactive solvents are various compounds such as 2-ethyl hexyl acrylate, 1,6-hexanediol diacrylate, trimethylolpropanetriacrylate, and the like.
The amount of polycarboxylic acid anhydride to be reacted with the caprolactone acrylate can be an amount sufficient to react with all of the hydroxyl groups; however, it may be desirable to use an amount of anhydride which is insufficient to react with all of the hydroxyl groups present in the caprolactone acrylate. This amount will vary and can be from about 0.1 to one anhydride equivalent or anhydride moiety for each hydroxyl equivalent or group present in the caprolactone acrylate, preferably from about 0.4 to one anhydride equivalent or anhydride moiety for each hydroxyl group present in the caprolactone acrylate, and more preferably from about 0.6 to one anhydride equivalent or anhydride moiety for each hydroxyl group. In a most preferred instance, one anhydride equivalent or anhydride moiety is charged for each hydroxyl equivalent or group initially present in the reaction mixture.
DESCRIPTION OF THE INVENTION
It has been found that novel, useful compounds can be prepared by reacting lactone acrylates, which are the reaction products of a lactone or mixture of lactones such as epsilon-caprolactone or a mixture of epsilon-caprolactone and epsilon-methyl-epsilon-caprolactone and a hydroxyalkyl acrylate such as hydroxyethyl acrylate or hydroxyethyl methacrylate, with an intramolecular polycarboxylic acid anhydride such as maleic anhydride. This reaction is depicted above in a generalized manner.
If desired, carboxylic acids can be reacted with the caprolactone acrylate via a condensation mechanism to yield monofunctional or polyfunctional compounds or mixtures thereof. These polyfunctional compounds can have single or multiple acrylate functionality and/or single or multiple carboxyl functionality. Specifically, when polyfunctional carboxylic acids are used, the resulting compound of this invention can have mono or multiple acrylate functionality and/or mono or multicarboxyl functionality. When monofunctional carboxylic acids or anhydrides, such as acetic anhydride, are used, the product will be an ester- or substituted ester-terminated molecule. However, the preferred reactant is an anhydride, which provides for more facile reaction conditions.
This compound and the other derivatives or adducts contemplated can be used in a variety of ways. For example, they can be used as radiation-curable monomers that will cure alone or in combination with other acrylates, diacrylates, triacrylates, multifunctional acrylates, vinyls, and the like, with variousforms of radiation, such as ultraviolet light, electron beam radiation, gamma radiation, X-rays, etc. These latter types of polymers are cured at times in the presence of a photoinitiator that generates free radicals, such as benzophenone, benzoin ethers, diethoxyacetophenone, etc. Of course, in the case of electron beam radiation and similar types of radiation, it is not necessary to use a photoinitiator. Other means of polymerizing molecules known to those skilled in the art can be utilized, if desired. For example, the compounds of the invention can be cured alone or in combination with other reactants by thermal means. To facilitate thermal cure, a peroxide may be included in the formulated system.
Where used in a coating system, it may be desirable to add driers to the coating system. These driers can be of various types, such as cobalt naphthenate, manganese naphthenate, iron hexoate, calcium octoate, and the like.
The compounds and/or polymers of this invention are useful in a variety of coating, ink, adhesive, and sealant applications, as dispersants, as water dispersible/soluble materials, as hardeners, as tougheners, etc. Of course, it is readily apparent that the trifunctional molecules prepared from maleic anhydride and lactone acrylate monomers can be used in a wide variety of ways since they contain acrylate, maleate, and carboxyl functionality. In addition, high functionality unsaturated molecules can be prepared from polyfunctional anhydrides and the lactone acrylates.
The molecules of this invention that contain maleic anhydride residues can also be combined with styrene to form useful radiation-cure coatings.
They also can be used as thickeners for unsaturated polyester/styrene systems that contain magnesium oxide, etc., wherein they will also provide or augment low profile characteristics, and/or other properties. The compounds of this invention can be used as the only thickener or in combination with other thickeners, such as carboxyl-terminated caprolactone polyols, carboxyl-containing vinyl copolymers, and the like.
If desired, two molecules of lactone acrylate can be used in the above-depicted reaction of a lactone acrylate with an anhydride, with the second molecule reacting with the carboxyl group of the indicated reaction product via a condensation mechanism to yield a diacrylate. This can be used in various ways, such as a cross-linking agent for coatings and so on.
In another embodiment of this invention, the carboxyl-terminated lactone acrylates can be reacted with a variety of mono- or polyhydric alcohols to form the corresponding esters, which are useful as flexibilizers for radiation-cure formulations, in other uses that require acrylates, such as oligomers and polymers, and as high-boiling solvents. A variety of alcohols can be used, as for example, methanol, which would yield the methyl ester of the lactone acrylate, ethanol, which would yield the ethyl ester of the lactone acrylate, propanol, iso-propanol, n-butanol, s-butanol, i-butanol, t-butanol, and so on. Useful polyhydric alcohols would include glucose, sucrose, glycerol, sorbitol, inositol, and so on.
In a special embodiment of the invention, the lactone acrylate can be reacted with acetic anhydride to form the methyl ester of the lactone acrylate or it can be reacted with various monocarboxylic acids to form a variety of esters. Although such esters are not acid-terminated, they are useful as acrylates in the preparation of polymers or oligomers than may be crosslinked or that can be used in radiation curable systems. In general, such novel compounds are useful as flexibilizers.
While a preferred embodiment of the invention contains two molecules of caprolactone, on the average, per acrylate group, useful products can have from one to twenty or more caprolactone units per acrylate group, or can be a mixture of compounds that contain from one to about twenty or more lactone units. In addition, these units could be other lactones such as beta-propiolactone, delta-valerolactone, delta-butyrolactone, zeta-enantholactone, eta-caprylolactone, and so on, or substituted lactones such as 6-methyl-epsilon-caprolactone, 3-methyl-epsilon-caprolactone, 5-methyl-epsilon-caprolactone, 5-phenyl-epsilon caprolactone, 4-methyl-delta-valerolactone, 3,5-dimethyl-epsilon caprolactone, and so on, or copolymers of such lactones, such as a copolymer of epsilon-caprolactone and epsilon-methyl-epsilon caprolactone, of epsilon-caprolactone and eta-caprylolactone, of delta-valerolactone and epsilon-methyl-epsilon-caprolactone, and so on. In addition, combinations of lactones and oxides such as ethylene oxide, propylene oxide, butylene oxide, and so on, can be used to make the "lactone acrylate" compounds. Of course, when desired, the lactone acrylate can be prepared from one or more lactones alone or in combination with one or more of the described oxides. In an embodiment of the invention, the lactone acrylate can be prepared by reacting a hydroxyalkyl acrylate and a mixture of caprolactone, diacid--such as adipic acid, and diol--such as 1,6-hexane diol. Also useful in place of, or in addition to, diols are polyols, such as triols, tetrols, and so on. If desired, one or more oxides can be included in the reaction mixture. Further types of lactone acrylate will be those described above that have been end-capped with one or more moles of an alkylene oxide or of a tetrahydrofuran. For example, the caprolactone acrylate
CH.sub.2 ═CHCOOCH.sub.2 CH.sub.2 O--[--CO(CH.sub.2).sub.5 --O--].sub.2 H
can be reacted with n molecules of ethylene oxide to produce the following molecule
CH.sub.2 ═CHCOOCH.sub.2 CH.sub.2 --O--[--CO(CH.sub.2).sub.5 --O--].sub.2 [--CH.sub.2 CH.sub.2 --O--].sub.n H
where n has a value of one to about ten or more. This oxide-capped molecule can be reacted with an anhydride to produce the molecules of this invention. If desired, before reacting the oxide-capped caprolactone acrylate with an anhydride, it could be further reacted with a lactone to form a block copolymer with alternating blocks that are the same or different in composition. Finally, the copolymeric acrylate would be reacted with an anhydride to produce the molecules of this invention.
Although a variety of lactones can be used, the preferred lactones to be used in the preparation of the caprolactone acrylates are epsilon-caprolactone and substituted epsilon-caprolactone. The most preferred lactone is epsilon-caprolactone.
The hydroxyalkyl acrylates that can be used to produce the lactone acrylate are 2-hydroxyethyl, 2-hydroxypropyl, 2-hydroxybutyl, 3-hydroxypropyl acrylate or methacrylate, diethylene glycol monoacrylate or monomethacrylate, glycerine or trimethylolpropane mono- or diacrylate or mono- or dimethacrylate, pentaerythritol mono-, di-, or triacrylate or mono-, di-, or trimethacrylate, glucose or sorbitol mono-, di-, tri-, tetra-, and penta-acrylate, or mono-, di-, tri-, tetra-, and pentamethacrylate, and the like. If desired, mixtures of one or more of these acrylates can be used in preparing the lactone acrylate of this invention.
Cyclic anhydrides of carboxylic acids are preferred for reaction with the lactone acrylates. However, if desired, mono- and polyfunctional carboxylic acids may be used wherein a condensation mechanism is employed. Anhydrides are preferred. Among the various anhydrides that can be used for the practice of this invention are maleic anhydride, succinic anhydride, phthalic anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, glutaric anhydride, cis- and trans-1,2-cyclohexane dicarboxylic anhydride, citraconic anhydride, itaconic anhydride, dodecenyl anhydride, isophthalic anhydride, hexachlorophthalic phthalic anhydride, chlorendic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic acid dianhydride, naphthoic anhydride, norbornene dicarboxylic acid anhydride, acetic anhydride, acrylic anhydride, methacrylic anhydride, or any other intramolecular anhydride including those having one or more anhydride groups and those having substituents thereon such as halogen atoms, alkyl, alkoxy, or aromatic groups, nitro, carboxyl, aryl, or any other group that will not unduly interfere with the reaction. In addition, when desired, mixtures of one or more anhydrides and/or carboxylic acids can be used. When the products of this invention are prepared, from about 0.1 to about one equivalent of anhydride can be used per equivalent of hydroxyl and it is preferred to use about 0.4 to about one equivalent of anhydride per equivalent of hydroxyl, and it is preferred to use from 0.6 to one equivalent of anhydride per equivalent of hydroxyl. In a most preferred instance, one anhydride equivalent or anhydride moiety is charged for each hydroxyl equivalent or group initially present in the reaction mixture.
Illustrative of the monofunctional carboxylic acid compounds that can be used, one can name pentanoic acid, hexanoic acid, octanoic acid, caprylic acid, capric acid, hendecanoic acid, lauric acid, tridecanoic acid, pentadecanoic acid, stearic acid, arachidic acid, behenic acid, benzoic acid, cerotic acid, 2-ethylhexanoic acid, naphthoic acid, myristic acid, palmitic acid, oleic acid, linoleic acid, linolenic acid, oleostearic acid, levulinic acid, ricinoleic acid, cinnamic acid, and the like, and mixtures of such acids.
Illustrative of the polyfunctional carboxylic acids that can be used, one can mention oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, suberic acid, azelaic acid, sebacic acid, brassylic acid, maleic acid, fumaric acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, tartaric acid, malic acid, mannaric acid, 1,4-cyclohexanedicarboxylic acid, 1,2-cyclohexanedicarboxylic acid, 1,4,5,6,7,7-hexachloro-5-norbornene-2,3-dicarboxylic acid, hexahydophthalic acid, galactaric acid, 4,5-cyclohexenedicarboxylic acid, 3,6-methylene- 4-cyclohexene-1,2-dicarboxylic acid, citric acid, and the like, as well as mixtures of these acids and mixtures of these acids with monocarboxylic acids. The carboxylic acids can be unsubstituted or they can be substituted with any group which will not significantly interfere with the reaction. Illustrative of suitable substituents are the halogens, nitro, alkoxy, alkyl, keto, and the like.
It is understood that by reacting acid chloride with lactone acrylates, certain products of this invention can also be made.
The anhydride-capped lactone acrylates of this invention can be used in many ways. These ways of utilizing the compounds include homopolymerization or copolymerization with a variety of other suitable acrylates, methacrylates, or other ethylenically unsaturated compounds that will undergo copolymerization by radiation reaction techniques. Suitable compounds for copolymerization include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary-butyl, tertiary-butyl, pentyl, neopentyl, isopentyl, hexyl, ethyl-hexyl, dodecyl, glycidyl, hydroxyalkyl, and so on, acrylates and methacrylates, acrylic and methacrylic acid, 2-polystyrylalkylmethacrylates as 2-polystyrylethylmethacrylate (Arco Chemical Co., Chemlink 4500), vinyl compounds such as vinyl acetate, vinyl chloride, styrene, acrylonitrile, methacrylonitrile, and the like, 1,6-hexanediol diacrylate, trimethylolpropane di- and triacrylate and methacrylate, pentaerythritol di-, tri-, and tetraacrylate, diethylene glycol diacrylate, esterdiol diacrylates, alkoxylated esterdiol diacrylates, caprolactone acrylates or methacrylates wherein caprolactone polyols (that are elsewhere described as in U.S. Pat. No. 3,169,945, for example) are esterified with acrylic or methacrylic acid, alkoxylated derivatives (i.e., end-capped) of the above-described caprolactone polyols that are esterified with acrylic or methacrylic acid, alkylene oxide polyols or monols that have been esterified with acrylic or methacrylic acid, reaction products of alkylene oxides with monols or polyols such as hydroxyalkyl acrylates or trimethylol propane, pentaerythritol, sorbitol, glucose, etc., that have been esterified with acrylic or methacrylic acid, poly(tetramethylene oxide) polyols that have been esterified with acrylic acid or methacrylic acid, epoxy acrylates, urethane acrylates, and the like.
A variety ofphotoinitiators can be utilized in the radiation-curing aspect of this invention. When acrylates or other unsaturated compounds are used, the usually used photoinitiators are the type that generate free radicals when exposed to radiation energy. Any of the known photoinitiators can be used. Illustrative of suitable photoinitiators one can mention 2,2-diethoxyacetophenone, 2- or 3- or 4-bromoacetophenone, 3- or 4-allyl-acetophenone, 2-acetonaphthone, benzaldehyde, benzoin, the alkyl benzoin ethers, benzophenone, benzoquinone, 1-chloroanthraquinone, p-diacetyl-benzene, 9,10-dibromoanthracene, 9,10-dichloroanthracene, 4,4-dichlorobenzophenone, thioxanthone, isopropyl-thioxanthone, methylthioxanthone, a, a, a,-trichloro-para-t-butyl acetophenone, 4-methoxybenzophenone, 3-chloro-8-nonylxanthone, 3-iodo-7-methoxyxanthone, benzaldehyde, carbazole, 4-chloro-4'-benzylbenzophenone, fluoroene, fluoroenone, 1,4-naphthylphenylketone, 1,3-pentanedione, 2,2-di-sec.-butoxy acetophenone, dimethoxyphenyl acetophenone, propiophenone, isopropylthioxanthone, chlorothioxanthone, xanthone, and the like, or any mixtures of these. The foregoing list is meant to be illustrative only and is not meant to exclude any suitable photoinitiators known to those skilled in the art. Those skilled in the art will know the concentrations at which photoinitiators are effectively employed and generally the concentration will not exceed 15 weight percent of the radiation-curable coating composition.
Those skilled in the art of photochemistry are fully aware that photoactivators can be used in combination with the aforementioned photoinitiators and that synergistic effects are sometimes achieved when such combinations are used. Photoactivators are well known in the art and require no further description to make known what they are and the concentrations at which they are effective. Nonetheless, one can mention as illustrative of suitable photoactivators, methylamine, tributylamine, methyldiethanolamine, 2-aminoethylethanolamine, allylamine, cyclohexylamine, cyclopentadienylamine, diphenylamine, ditolylamine, trixylylamine, tribenzylamine, n-cyclohexylethyleneimine, piperidine, N-methylpiperazine, 2,2-dimethyl-1,3-bis(3-N-morpholinyl)-propionyloxypropane, and the like, or any combination of these.
The formulations of this invention can be cured by ionizing or non-ionizing radiation means including, but not limited to, ultraviolet light, gamma radiation, and electron beam radiation. These curing methods and the equipment that can be used for them are well known to those skilled in the art. When the binder is to be cured by non-ionizing radiation, the presence of a photoinitiator therein is desirable. Suitable sources of radiation include mercury, xenon, carbon arc lamps, sunlight, radioactive sources, etc. Exposures may be from less than about 1 second to 10 minutes or more, depending upon the amounts of particular polymerizable materials and photoinitiator being utilized and depending upon the radiation source and distance from the source, and the thickness of the coating to be cured. The compositions may also be photopolymerized by exposure to electron beam radiation. Generally speaking the dosage necessary is from less than 1 megarad to 100 megarads or more.
The compositions of this invention may also include one or more thermoplastic resins free from any radiation-curable, unsaturated bond. Among useful thermoplastic resins for this purpose are vinyl chloride-vinyl acetate copolymers and other vinyl chloride resins, cellulose nitrate, cellulose acetate and other polyester resins, polyvinyl alcohol resins, and other cellulose derivatives, thermoplastic polyurethane resins, polyamide resins, polycaprolactone, polyvinylidene chloride, polyacrylates and other acrylic resins. The addition of such a thermoplastic resin is effective in balancing hardness, toughness, flexibility and other properties of the product, as well as providing sag control and viscosity control.
Although many radiation-cure coating systems are solvent-free, they may contain conventional solvents such as cyclohexanone, 1,1,1-trichloroethane, toluene, methyl isobutyl ketone, methyl amyl ketone, ethoxyethyl acetate, methylene chloride, and the like, and mixtures of these solvents, such as, for example a 2:2:1 mixture of methyl isobutyl ketone, toluene and cyclohexane.
The coating compositions may preferably include additives in conventional quantities, such as oils, particularly silicone oil, surfactants such as silicone-alkylene oxide copolymers, e.g., L-7604, L-7610, etc., commercially available from Union Carbide Corporation, silicone oil containing aliphatic epoxide groups, fluorocarbon surfactants such as FC-171 commercially available from 3M Commercial Chemicals Division and FC-430 and FC-431 also commercially available from 3M Commercial Chemicals Division, Modaflow commercially available from Monsanto Co., and other similar type compounds that are used to improve the flow and leveling characteristics of coatings.
In an aspect of the thermally-cured coatings portion of this invention, the anhydride-capped lactone acrylates of this invention can be combined with the various acrylates mentioned above and the free radical initiators, such as benzoyl peroxide, lauroyl peroxide, and the like, that yield free radicals when heated, to yield highly useful systems. In this case, no photoinitiators are necessary unless one wishes to combine thermal and radiation curing.
The coating compositions of this invention can contain various additives that are known to those skilled in the art. Such additives include, pigments, colorants, dyes, defoamers, thickeners, preservatives, mildew inhibitors, anti-sag agents, anti-settling agents, and the like.
The invention is further described in the examples which follow. All parts and percentages are by weight unless otherwise specified.
In the examples which follow, the cured coating compositions were evaluated according to the following procedures:
Forward Impact Resistance: a measure of the ability of a cured film coating to resist rupture from a falling weight. A Gardner Impact Tester using an eight-pound dart was used to test film coatings cast and cured on steel panels. The dart was raised to a given height in inches and dropped onto the coating side of the coated steel panel. The inches times pounds, designated inch-pounds, absorbed by the film without rupturing was recorded as the film's forward impact resistance.
Pencil Hardness (ASTM D-3363-74): pencil leads of increasing hardness values were forced against the film coating surface in a precisely defined manner until one pencil lead cut through the surface of the film coating. The surface hardness was considered as the hardest pencil grade which just failed to cut through the film coating surface. The pencil leads, in order of softest to hardest, were reported as follows: 6B, 5B, 4B, 3B, 2B, B, HB, F, H, 2H, 3H, 4H, 5H, 6H, 7H, 8H, and 9H.
Solvent Resistance: a measure of the resistance of the cured film to attack by acetone and was reported as the number of rubs or cycles of acetone-soaked cheesecloth required to remove one-half of a cured film from the test area. This test was performed by stroking the cured film with acetone-soaked cheesecloth until that amount of film coating was removed. The number of cycles required to remove this amount of coating was a measure of the coating's solvent resistance.
Reverse Impact Resistance: a measure of the ability of a cured film coating to resist rupture from a falling weight. A Gardner Impact Tester using an eight-pound dart was used to test film coatings cast and cured on steel panels. The dart was raised to a given height in inches and dropped onto the uncoated side of the coated steel panel. The inches times pounds, designated inch-pounds, absorbed by the film without rupturing was recorded as the film's reverse impact resistance.
Crosshatch Adhesion: a lattice pattern with either six or eleven cuts in each direction was made in the coating film to the substrate and pressure-sensitive adhesive tape was applied over the lattice pattern and then removed. The adhesion was evaluated by comparison with descriptions and illustrations, as more fully detailed in ASTM D-3359-78.
GLOSSARY OF MATERIALS USED IN EXAMPLES
1. TONE Monomer M-100. A caprolactone acrylate with an average molecular weight of about 344 and marketed by Union Carbide Corp.
2. Uvithane 893. A urethane acrylate marketed by Thiokol. It is a viscous liquid that has a viscosity of 900 to 2,200 poise at 120° F.
3. Irgacure 184. A free radical-generating photoinitiator that is marketed by Ciba-Geigy. It is stated to be 1-hydrocycyclohexyl phenyl ketone.
4. L-5410. A silicone/alkylene oxide copolymer formerly marketed under that designation by Union Carbide Corporation and now marketed as L-7610 under the SILWET trademark by Union Carbide Corporation.
5. L-7604 and L-7610 are silicone/alkylene oxide copolymers marketed by Union Carbide Corporation. The silicone/alkylene oxide polymers are modified dimethylpolysiloxanes.
6. Esterdiol 204. A methylolated proprionate diol marketed by Union Carbide Corporation.
EXAMPLE 1
One hundred grams of TONE Monomer M-100 were added to a 300 milliliter reaction flask equipped with a stirrer, air inlet and an air outlet, and a thermometer. The M-100 was heated to 110° C. with stirring and an air blanket. When the flask temperature reached 100° C., 24.7 grams of succinic anhydride were added slowly to avoid an exothermic reaction. Addition of the anhydride lowered the temperature about 7° C. The mixture of chemicals was heated for four hours at 117°-120° C. and at 130° C. for one hour. The product was cooled and stored. Analysis indicated that it had an acid number of 124, which would correspond to an average molecular weight of 452, which is quite close to the theoretical molecular weight of 444 for the expected product.
EXAMPLE 2
Forty-nine grams of maleic anhydride and 172 grams of M-100 monomer were combined in a glass, four-neck reaction flask equipped with a thermometer,stirrer, an air inlet and an air outlet. The reactants were heated for four hours at 125° C., an hour at 125° to 144° C., and 3.5 hours at 130° to 135° C. The product was cooled to room temperature and the acid number was found to be 115. Its viscosity was 560 cp when measured at 60 rpm with a UK LV8 viscometer and a #7 spindle.
EXAMPLES 3 to 7
The ingredients shown in Table I were placed in amber-colored, glass bottles, mixed well and cast onto Bonderite 37 steel panels with a No. 20 wire-wound rod and cured with a 300 watt/inch Fusion Systems ultraviolet light curing unit. Properties of cured film and plaques are also shown in Table I.
              TABLE I                                                     
______________________________________                                    
           Example                                                        
           3     4        5       6*    7                                 
______________________________________                                    
Ingredients                                                               
Example 2 Product                                                         
             --      --       2.00  --    10.0                            
M-100 Monomer                                                             
             --      2.00     --    10.0  --                              
Tetraethylene glycol                                                      
             4.00    3.20     3.20  --    --                              
diacrylate                                                                
Uvithane 893 6.00    4.80     4.80  --    --                              
Irgacure 184 0.40    0.40     0.40  0.40  0.40                            
L-5410       0.05    0.05     0.05  0.05  0.05                            
Properties After Cure                                                     
Double Acetone Rubs                                                       
             >100    >100     >100  40    50                              
Pencil Hardness                                                           
             H       H        2H    <6B   6B                              
Gardner Impact                                                            
Direct, in. lbs.                                                          
             275     150      250   320   200                             
Reverse, in. lbs.                                                         
             200     125      225   320   100                             
______________________________________                                    
 *This was a very soft system that had a rubbery, highfriction feel after 
 cure.
From these data, it is apparent that the product of Example 2 improves the hardness of the urethane acrylate system (Example 5 vs. Example 3) more than the TONE Monomer M-100 (Example 3 vs. Example 4). In addition, the product of Example 2 has effectively not altered the impact resistance of the urethane acrylate whereas the M-100 has caused a marked decrease in impact characteristics. Thus, the product of Example 2 achieved both an increase in hardness and in flexibility/impact resistance which is not expected, in that one property usually decreases when the other property increases. The improvement in hardness is apparent when the data of Examples 6 and 7 are compared. The homopolymer of TONE Monomer M-100 is <6B in hardness, indicating a very soft coating, whereas the homopolymer of the Example 2 product (Example 7) is 6B in hardness. Although it is readily apparent that there is an improvement of the Example 7 coating over that of Example 6 coating, to emphasize this difference, the systems of Examples 6 and 7 were subjected to 5 passes under the ultraviolet light source. After this treatment, the coating of Example 6 was still <6B in hardness, whereas the coating of Example 7 was 4B in hardness, indicating that there was at least a "three-pencil" hardness difference in the coatings.
EXAMPLES 8-20
In the same manner as described in Examples 3 to 7, the systems shown in Table II were prepared, cured, and tested. The cured coatings were then evaluated, and they had the properties described below. The purpose in these studies (Ex. 8-15 and 18/19) was to demonstrate that the newly developed product of Example 2 did not decrease hardness of a very hard, radiation-cured system as much as M-100 monomer. The other examples are for the purpose of demonstrating that useful radiation-cured products can be derived from the Example 2 product and a variety of other acrylates.
                                  TABLE II                                
__________________________________________________________________________
           Example                                                        
           8   9   10  11  12  13  14  15  16  17  18  19  20             
__________________________________________________________________________
Ingredients                                                               
M-100 Monomer                                                             
           1.00                                                           
               2.00                                                       
                   3.00                                                   
                       4.00                                               
                           --  --  --  --  --  --  2.00                   
                                                       --  10.0           
Example 2 Product                                                         
           --  --  --  --  1.00                                           
                               2.00                                       
                                   3.00                                   
                                       4.00                               
                                           1.28                           
                                               3.85                       
                                                   --  2.00               
                                                           2.00           
13379-83-3**                               --  --  3.00                   
                                                       3.00               
                                                           2.00           
44-OWS-52***                               --  --  --  --  2.00           
Acetoner C-488.sup.+                       --  --  --  --  2.00           
TMP-Triacrylate*                                                          
           9.00                                                           
               8.00                                                       
                   7.00                                                   
                       6.00                                               
                           9.00                                           
                               8.00                                       
                                   7.00                                   
                                       6.00                               
                                           9.00                           
                                               7.00                       
                                                   5.00                   
                                                       5.00               
                                                           1.00           
Irgacure 184                                                              
           0.20                                                           
               0.20                                                       
                   0.20                                                   
                       0.20                                               
                           0.20                                           
                               0.20                                       
                                   0.20                                   
                                       0.20                               
                                           0.20                           
                                               0.20                       
                                                   0.20                   
                                                       0.20               
                                                           0.20           
L-5410     ←0.04→              ←0.04→             
Properties After Cure*                                                    
Double Acetone Rubs                                                       
           >100                                                           
               >100                                                       
                   >100                                                   
                       >100                                               
                           >100                                           
                               >100                                       
                                   >100                                   
                                       >100                               
                                           >100                           
                                               >100                       
                                                   >100                   
                                                       >100               
                                                           >100           
Pencil Hardness                                                           
           5H  4H  H   H   5H  4H  3H  4H  4H  4H  3H  5H  H              
Percent Adhesion                                                          
           90  85  95  90  99  98  98  98  98  99  98  98  10             
Gardner Impact                                                            
Direct, in. lbs                                                           
           10  15  15  15  15  15  15  15  15  25  25  25  25             
Reverse, in. lbs                                                          
            <5  <5  <5  <5  <5  <5  <5  <5  <5  <5  <5  <5  <5            
__________________________________________________________________________
 *Trimethylolpropane triacrylate.                                         
 **TONE0405 tetraacrylate. [The reaction product of 4 moles of acrylic aci
 and one mole of a 540 molecular weight caprolactone triol                
 ***(TONE0305)] M100 that has been endcapped with methyl isocyanate.      
 .sup.+ Diacrylate of the fourmole ethoxylate of Esterdiol204.
It is apparent from the above data that the product of Example 2 is much more effective in maintaining hardness than other additives such as M-100 monomer. This is especially apparent when Examples 10 and 11 are compared with Examples 14 and 15, and when Examples 18 and 19 are compared.
EXAMPLE 21
Ninety-eight grams of maleic anhydride and 344 grams of TONE Monomer M-100 were combined in a glass, four-neck reaction flask equipped with a thermometer, a stirrer, an air inlet and an air outlet. The reactants were heated for 9.75 hours at 130° to 137° C. The product was then cooled to room temperature and the acid number was found to be 115. The product had a viscosity of 556 cp when measured at 30 rpm with a UK LVB viscometer equipped with a #6 spindle.
EXAMPLES 22-27
The ingredients shown in Table III were placed in amber-colored, glass bottles, mixed well, and cast onto Bondrite #37 steel panels with a #20 wire-wound rod, and cured using one, three or five passes under a 300 watt per inch Fusion Systems ultraviolet light curing unit.
              TABLE III                                                   
______________________________________                                    
        Examples                                                          
        22    23      24      25    26    27                              
______________________________________                                    
Ingredients                                                               
Example 21                                                                
          3.00    3.00    3.00  5.00  5.00  5.00                          
Product                                                                   
TMP Tri-  7.00    7.00    7.00  7.00  7.00  --                            
acrylate                                                                  
Irgacure 184                                                              
          0.20    0.30    0.50  0.30  0.50  0.25                          
L-7604    0.04    0.04    0.04  0.04  0.04  0.02                          
Properties                                                                
After One-                                                                
Pass Cure                                                                 
Double Ace-                                                               
          >100    >100    >100  >100  >100  25                            
tone Rubs                                                                 
Pencil Hardness                                                           
          H       2H      4H    2H    3H    <6B                           
% X-Hatch 0       15      5     35    0     100                           
Adhesion                                                                  
Gardner Impact                                                            
Direct, in. lbs                                                           
          15      15      15    25    25    75                            
Reverse, in. lbs                                                          
          <5      <5      <5    <5    <5    50                            
Properties                                                                
After Three-                                                              
Pass Cure                                                                 
Double Ace-                                                               
          >100    >100    >100  >100  >100  29                            
tone Rubs                                                                 
Pencil Hardness                                                           
          3H      4H      4H    4H    3H    <6B                           
% X-Hatch 25      50      30    30    12    100                           
Adhesion                                                                  
Gardner Impact                                                            
Direct, in. lbs                                                           
          15      15      15    25    25    75                            
Reverse, in. lbs                                                          
          <5      <5      <5    < 5   <5    50                            
Properties                                                                
After Five-                                                               
Pass Cure                                                                 
Double Ace-                                                               
          >100    >100    >100  >100  >100  35                            
tone Rubs                                                                 
Pencil Hardness                                                           
          4H      4H      4H    4H    3H    3B                            
% X-Hatch 90      90      50    90    16    100                           
Adhesion                                                                  
Gardner Impact                                                            
Direct, in. lbs                                                           
          15      15      15    25    25    75                            
Reverse, in. lbs                                                          
          <5      <5      <5    <5    <5    50                            
______________________________________
These examples demonstrate that systems containing the maleic anhydride adduct of a caprolactone acrylate respond to both increasing levels of photoinitiator and increasing levels of radiation or multiple passes under the light source. Variables such as these are altered when system/cure is optimized. Properties of the systems improve as either of these variables is increased.
EXAMPLES 28-33
The ingredients shown in Table IV were combined in a glass, four-neck reaction flask equipped with a thermometer, a stirrer, an air inlet and an air outlet. The reactants were heated at the indicated temperatures for the indicated times. An air flow, which blanketed the reacting ingredients was maintained during the entire reaction time. The reactants were cooled and the final acid number and viscosity were determined.
              TABLE IV                                                    
______________________________________                                    
             Example                                                      
Ingredients    28     29     30   31   32   33                            
______________________________________                                    
Maleic Anhydride                                                          
                39.2   24.5   49.0                                        
                                   19.6                                   
                                        9.6  49.0                         
Phthalic Anhydride                                                        
                14.8   37.0  --   --   --   --                            
M-100 Monomer  172.0  172.0  --   --   --   --                            
Caprolactone Acrylate*                                                    
               --     --     --   160.0                                   
                                       --   --                            
Caprolactone Acrylate**                                                   
               --     --     --   --   251.2                              
                                            --                            
Placcel FM-2.sup.+                                                        
               --     --     179.0                                        
                                  --   --   --                            
Placcel FM-1.sup.++                                                       
               --     --     --   --   --   122.0                         
Reaction Time, hr.                                                        
                3      2     2.25 1.50  4.0  1.0                          
Reaction Temp. °C.                                                 
               125    125    125  125  125  125                           
Acid No.       121.2  121.3  125.1                                        
                                   56.2                                   
                                        48.6                              
                                            147.8                         
Viscosity, 25° C. cp                                               
               630    860    490  Solid                                   
                                       Solid                              
                                            280                           
______________________________________                                    
 *The reaction product of 6 moles of epsiloncaprolactone and one mole of  
 HEA.                                                                     
 **The reaction product of 10 moles of epsiloncaprolactone and one mole of
 HEA.                                                                     
 .sup.+ The twomole caprolactone adduct of hydroxyethylmethacrylate, sold 
 by Daicel.                                                               
 .sup.++ The onemole caprolactone adduct of hydroxyethylmethacrylate, sold
 by Daicel.
The products of these examples demonstratethe preparation of a variety of carboxyl-terminated acrylate monomers. Examples 28 and 29 are examples of products prepared from mixtures of an unsaturated anhydride (maleic) and a saturated anhydride (phthalic). Such products can be used to alter the final degree of crosslinking of systems in which they are utilized. The products of Examples 31 and 32 are based on relatively high molecular weight caprolactone acrylates and are for systems in which a high degree of flexibility or other specialized property is desired. These long-chain molecules will provide a plasticizing, softening, or other special effect when used in a variety of systems that can be cured by radiation or heat. Examples 30 and 33 demonstrate that carboxyl-functional methacrylates can be prepared. These methacrylates will usually provide higher hardness along with flexibility than the corresponding acrylates.
EXAMPLES 34-42
The ingredients shown in Table V were placed in glass bottles and well mixed. They were then coated onto Bonderite 37 steel panels with a No. 20 wire-wound rod and exposed to a 300 watt/inch ultraviolet light source at 10 fpm.
                                  TABLE V                                 
__________________________________________________________________________
            Example                                                       
            34  35    36   37     38    39    40    41   42               
__________________________________________________________________________
Ingredients                                                               
Example 21 Product                                                        
            --  --    5.0   --    --    --    --    --   --               
Example 28 Product                                                        
            10.0                                                          
                --    --    5.0   --    --    --    --   --               
Example 29 Product                                                        
            --  10.0  --    --    5.0   4.0   --    --   --               
Example 31 Product                                                        
            --  --    --    --    --    --    --    10.0 3.5              
TMP-Triacrylate                                                           
            --  --    5.0   5.0   5.0   --    --    --   6.5              
1,6-Hexanedioldiacrylate                                                  
            --  --    --    --    --    6.0   6.0   --   --               
M-100       --  --    --    --    --    --    4.0   --   --               
Irgacure 184                                                              
            0.5 0.5   0.5   0.5   0.5   0.5   0.5   0.5  0.5              
L-7604      0.04                                                          
                0.04  0.04  0.04  0.04  0.04  0.04  0.04 0.04             
Properties After Cure                                                     
Acetone Double rubs                                                       
            15  14    >100  >100  >100  >100  >100  12   >100             
Pencil Hardness                                                           
            6B  6B    H     H     H     F     3B    6B   H                
% X-Hatch Adhesion                                                        
            100 100   0     0     0     0     0     0    0                
Gardner Impact                                                            
Direct, in. lbs.                                                          
            50  75    25    25    25    25    25    320  15               
Reverse, in. lbs.                                                         
            50  50    <5    <5    <5    <5    <5    175  <5               
__________________________________________________________________________
The results indicate that the carboxyl-terminated acrylates do respond to polymerization when subjected to UV light in the presence of a free radical-generating photoinitiator. Examples 36, 37, and 38 indicate that similar properties are obtained when either the phthalate/maleate acrylate mixture or the maleate acrylate alone is used in the particular system investigated. (Results may be different when these products used are in other formulated systems.) Examples 39 and 40 compare the results obtained when a system containing a caprolactone acrylate (Ex. 40) is compared with a mixed phthalate/maleate caprolactone acrylate (Ex. 39). It is readily apparent that a significantly harder coating is obtained with the Ex. 39 system.
EXAMPLES 43-51
The examples shown in Table VI describe the combination and radiation (ultraviolet light) cure of carboxyl-terminated caprolactone acrylates prepared in previous examples and other acrylates such as the diacrylate 1,6-hexanediol diacrylate (HD Diacrylate), the triacrylate trimethylolpropane triacrylate (TMP triacrylate), and an epoxy acrylate (Celrad 3700*) or mixtures of such acrylates. The ingredients listed were placed in glass bottles and well mixed. They were warmed to rapidly effect dissolution of the Irgacure 184 photoinitiator.
The solutions were then coated onto Bonderite 37 steel panels with a #20 wire-wound rod and exposed to a 300 watt per inch ultraviolet light source at 10 fpm.
                                  TABLE VI                                
__________________________________________________________________________
           Example                                                        
           43    44    45  46    47    48    49    50    51               
__________________________________________________________________________
Ingredients                                                               
Example 29 Product                                                        
           --    --    --  --    --    --    --    --    2.50             
Example 30 Product                                                        
           9.46  --    --  --    --    --    --    --    --               
Example 31 Product                                                        
           --    5.5   --  --    --    --    2.50  --    --               
Example 32 Product                                                        
           --    --    9.46                                               
                           --    3.50  --    --    2.50  --               
Example 33 Product                                                        
           --    --    --  9.46  --    --    --    --    --               
TMP Triacrylate                                                           
           --    4.5   --  --    6.5   --    --    --    --               
HDD Diacrylate                                                            
           --    --    --  --    --    2.46  1.81  1.81  1.81             
Celrad 3700                                                               
           --    --    --  --    --    7.0   5.15  5.15  5.15             
Irgacure 184                                                              
           0.50  0.50  0.50                                               
                           0.50  0.50  0.50  0.50  0.50  0.50             
L-7604     0.04  0.04  0.04                                               
                           0.04  0.04  0.04  0.04  0.04  0.04             
Properties After Cure                                                     
Acetone Dbl Rubs                                                          
           12    >100  10  25    >100  >100  >100  >100  >100             
Pencil Hardness                                                           
           6B    2B    6B  6B    H     H     H     H     H                
% X-Hatch Adhesion                                                        
           100   0     100 100   0     0     0     0     0                
Gardner Impact                                                            
Direct, in. lbs.                                                          
           320   15    320 320   25    25    25    25    25               
Reverse, in. lbs.                                                         
           320   <5    320 200   <5    <5    <5    <5    <5               
__________________________________________________________________________
These results indicate that the carboxyl-terminated acrylates of this invention do respond to polymerization when subject to UV light in the presence of a free radical photoinitiator. The results further indicate that the compounds of the invention can be combined with other commercially available acrylates and the resultant combinations yield well-cured coating systems that would be useful in a variety of ways, e.g., in coatings, inks, adhesives, and sealants. It is expected that the carboxyl functionality of the compounds of this invention will improve the pigment dispersion qualities of other acrylates and thus will have utility as pigment dispersion aids.
EXAMPLES 52-55
The ingredients listed in Table VII were combined in a glass, four-neck reaction flask equipped with a thermometer, a stirrer, and an air inlet and outlet. The reactants were heated at the indicated temperatures for the indicated times. An air flow, which blanketed the reacting ingredients, was maintained during the entire reaction time. The reactants were cooled and the final acid number and viscosity were determined.
The examples described use the following ingredients in the equivalent ratios indicted.
Example 52: 0.25 equivalent of M-100 and 0.25 equivalent of methyltetrahydrophthalic anhydride.
Example 53: 0.25 equivalent of M-100 and 0.25 equivalent of hexahydrophthalic anhydride.
Example 54: 0.25 equivalent of M-100 and 0.25 equivalent of phthalic anhydride.
Example 55: 0.375 equivalent of M-100 and 0.125 equivalent of hexahydrophthalic anhydride and 0.25 equivalent of phthalic anhydride.
              TABLE VII                                                   
______________________________________                                    
               Example                                                    
               52    53      54      55                                   
______________________________________                                    
Ingredients                                                               
Methyltetrahydrophthalic                                                  
                 41.25   --      --    --                                 
Anhydride                                                                 
Hexahydrophthalic Anhydride                                               
                 --      38.50   --    19.25                              
Phthalic Anhydride                                                        
                 --      --      37.0  37.0                               
M-100 Monomer    86.0    86.0    86.0  129.0                              
Reaction Conditions                                                       
Reaction Time, hr.                                                        
                 3       2.5     1     3.5                                
Reaction Temperature, °C.                                          
                 115     130     125   125                                
Analysis                                                                  
Acid Number      109     115     107   114                                
Viscosity, cp (25° C.)                                             
                 40790   1870    1263  1690                               
______________________________________
These examples described the preparation pf a variety of carboxyl-terminated caprolactone acrylate monomers, including preparation of a mixed anhydride-capped adduct.
EXAMPLES 56-60
These examples describe the blending and radiation curing of mixtures of a carboxyl-terminated caprolactone acrylate and the non-acrylate, ethylenically unsaturated compounds styrene and vinyl pyrrolidone. Example 27 is repeated since it functions as a control with no styrene or vinyl pyrrolidone.
The ingredients shown in Table VIII were placed in amber-colored, glass bottles, mixed well, and cast onto Bonderite 37 steel panels with a #20 wire-wound rod. The liquid coatings were then cured with one pass under a 300 watt per inch Fusion Systems ultraviolet light curing unit.
              TABLE VIII                                                  
______________________________________                                    
           Example                                                        
           27   56     57       58   59   60                              
______________________________________                                    
Ingredients                                                               
Example 21 Product                                                        
             5.00   8.5    7.5    7.5  9.0  8.5                           
Styrene      --     1.0    2.0    1.5  --   --                            
Vinyl pyrrolidone                                                         
             --     --     --     0.5  0.5  1.0                           
Irgacure 184 0.25   0.5    0.5    0.5  0.5  0.5                           
L-7610       0.04    0.04   0.04   0.04                                   
                                        0.04                              
                                             0.04                         
Properties After Cure                                                     
Acetone Dbl Rubs                                                          
             25     35     35      35   35   35                           
Pencil Hardness                                                           
             <6B    <6B    5B     4B   <6B  4B                            
% X-Hatch Adhesion                                                        
             100    100    100    100  100  100                           
Gardner Impact                                                            
Direct, in. lb.                                                           
             75     75     100    100  100  100                           
Reverse, in. lb.                                                          
             50     50     75     100   25   25                           
______________________________________
These examples demonstrate that the ethylenically unsaturated compounds styrene and vinyl pyrrolidone can be reacted with the carboxyl-terminated caprolactone acrylates of this invention and that they can be used to alter the hardness, solvent resistance, and impact resistance of the cured compounds of this invention.
EXAMPLES 61-72
These examples, shown in Table IX, compare the cured properties of formulations that contain carboxyl-terminated caprolactone acrylates (Examples 61, 63, 65, 66, 69, and 70) with those of formulations that contain the starting point caprolactone acrylates (Examples 62, 64, 67, 68, 71, and 72) that were used to make to carboxyl-terminated products of this invention.
                                  TABLE IX                                
__________________________________________________________________________
           Example                                                        
           61 62 63 64 65 66  67 68 69 70  71 72                          
__________________________________________________________________________
Ingredients                                                               
Example 30 Prod.                                                          
           10.0                                                           
              -- -- -- 8.0                                                
                          7.0 -- -- -- --  -- --                          
Example 36 Prod.                                                          
           -- -- 10.0                                                     
                    -- -- --  -- -- 8.0                                   
                                       7.0 -- --                          
Placcel FM-2                                                              
           -- 10.0                                                        
                 -- -- -- --  8.0                                         
                                 7.0                                      
                                    -- --  -- --                          
Placcel FM-1                                                              
           -- -- -- 10.0                                                  
                       -- --  -- -- -- --  8.0                            
                                              7.0                         
TMP Triacrylate                                                           
           -- -- -- -- -- 1.0 -- 1.0                                      
                                    -- 1.0 -- 1.0                         
UVITHANE 893                                                              
           -- -- -- -- 2.0                                                
                          2.0 2.0                                         
                                 2.0                                      
                                    2.0                                   
                                       2.0 2.0                            
                                              2.0                         
Irgacure 184                                                              
           0.40                                                           
              0.40                                                        
                 0.40                                                     
                    0.40                                                  
                       .40                                                
                          .40 .40                                         
                                 .40                                      
                                    .40                                   
                                       .40 .40                            
                                              .40                         
L-5410     0.05                                                           
              0.05                                                        
                 0.05                                                     
                    0.05                                                  
                       .05                                                
                          .05 .05                                         
                                 .05                                      
                                    .05                                   
                                       .05 .05                            
                                              .05                         
Properties After Cure                                                     
Acetone Double                                                            
           6  2  18 2  40 >100                                            
                              2  20 45 >100                               
                                           2  >100                        
Rubs                                                                      
Pencil Hardness                                                           
           -- -- -- -- -- HB  -- -- -- H   -- 2B                          
% X-Hatch Adhesion                                                        
           -- -- -- -- -- 100 -- -- -- 100 -- 100                         
Gardner Impact                                                            
Direct, in. lbs                                                           
           -- -- -- -- -- 25  -- -- -- 25  -- 25                          
Reverse, in. lbs                                                          
           -- -- -- -- -- 25  -- -- -- 25  -- 15                          
__________________________________________________________________________
 NOTE:                                                                    
 The Example 30 product is the reaction product of one equivalent of      
 Placcel FM2 and one equivalent of maleic anhydride, and the Example 31   
 product is the reaction product of one equivalent of Placcel FM1 and one 
 equivalent of maleic anhydride.
These results indicate that the cured compositions containing a product of this invention have improved properties over similar compositions that have this product deleted and replaced with the starting caprolactone acrylate. Properties such as solvent resistance, hardness, and impact resistance are improved. In those instances where properties other than solvent resistance (Acetone Double Rubs) were not determined, the coatings were not deemed as being of sufficient merit to warrant further investigation. It should be kept in mind that the above examples are examples that demonstrate that properties are different (i.e., improved when the compounds of this invention are used) rather than working examples of optimized systems or systems that might be used in commercial practice. However, this statement is not meant to imply that the examples are without merit nor that they could not be used in commercial practice.
EXAMPLE 73
This example demonstrates that low temperatures can be used to prepare the compositions of this invention. In this example, the reaction was carried out at 65° to 70° C.
Thirty-two and six-tenths grams of maleic anhydride and 114.6 grams of M-100 caprolactone acrylate [0.33 equivalent of each] were placed in a four-neck, glass reaction flask equipped with a thermometer, a stirrer, an air inlet and an air outlet. The reactants were heated at 65°-70° C. for three hours, during which time the reactants were blanketed with an air flow. After this reaction time, the product was cooled and stored. It had a viscosity of 314 cp at 25° C., a Gardner color of 2, and an acid number of 125.
Examples 74, 75 and Examples 76 and 77
Examples 74 and 75, shown in Table X, deal with the preparation of carboxyl-terminated caprolactone acrylates that are prepared from mixtures of anhydrides.
The same equipment as described in the previous example was used. The reactor contents, listed below, were heated to 125° C. to solubilize the anhydrides and then lowered to 100° C. and maintained at that temperature for 13 hours. After that time the reaction product was cooled to room temperature, properties were determined, and used in radiation cure systems.
              TABLE X                                                     
______________________________________                                    
                   Example                                                
                   74    75                                               
______________________________________                                    
Ingredients                                                               
Itaconic Anhydride    28     18.7                                         
Maleic Anhydride     --      16.3                                         
Phthalic Anhydride    37     24.6                                         
M-100                172     172                                          
Properties of Reaction Product                                            
Acid Number          134     125                                          
Viscosity, cp (25° C.)                                             
                     1586    908                                          
______________________________________
In Examples 76 and 77, the radiation-cure coating systems were formulated from the ingredients shown in Table XI by placing the compounds in amber colored glass bottles, mixing well, and then coating onto Bonderite 37 steel panels with a #20 wire-wound rod. They were then cured with a 300 watt/inch Fusions Systems ultraviolet light source at a rate of 10 fpm.
              TABLE XI                                                    
______________________________________                                    
                   Example                                                
                   76    77                                               
______________________________________                                    
Ingredients                                                               
Example 74 Product   10.0    --                                           
Example 75 Product   --      10.0                                         
Irgacure 184         0.50    0.50                                         
L-7604               0.04    0.04                                         
Properties of UV-cured Coatings                                           
Acetone Double Rubs  30      38                                           
Pencil Hardness      5B      5B                                           
% Crosshatch Adhesion                                                     
                     100     100                                          
Gardner Impact, inch-pounds                                               
Direct               200     100                                          
Reverse              100     <50                                          
______________________________________
This demonstrates that the adducts respond to ultraviolet light cure and that they have utility in radiation curable coatings, adhesives, inks, and sealants.
EXAMPLES 78-85
These examples demonstrate that the compounds of this invention can be combined with urethane acrylates and other acrylates to improve coating properties such as hardness and impact resistance. In addition, the examples point out that the compounds of this invention give improvements over those obtained when M-100, a caprolactone acrylate, is added to the formulation at the same level.
The ingredients shown in Table XII were placed in amber colored glass bottles, mixed, and coated onto Bonderite 37 steel panels with a #20 wire-wound rod. The liquid coatings were then cured with a 300 watt/inch Fusion systems ultraviolet light source at 50 feet per minute.
                                  TABLE XII                               
__________________________________________________________________________
       Example                                                            
           78  79 80 81 82  83  84  85                                    
__________________________________________________________________________
Ingredients                                                               
Example 21 Product                                                        
           --  -- 3.24                                                    
                     -- 2.00                                              
                            --  3.00                                      
                                    --                                    
Example 29 Product                                                        
           --  -- -- -- --  --  --  3.00                                  
Cargill XP-1512*                                                          
           9.8 6.54                                                       
                  6.54                                                    
                     6.54                                                 
                        6.54                                              
                            5.00                                          
                                5.00                                      
                                    5.00                                  
TMP Triacrylate                                                           
           --  -- -- 1.24                                                 
                        1.24                                              
                            1.78                                          
                                1.78                                      
                                    1.78                                  
M-100      --  3.24                                                       
                  -- 2.00                                                 
                        --  3.00                                          
                                --  --                                    
Vicure 10**                                                               
           0.20                                                           
               0.20                                                       
                  0.20                                                    
                     0.20                                                 
                        0.20                                              
                            0.20                                          
                                0.20                                      
                                    0.20                                  
Properties After Cure                                                     
Double Acetone Rubs                                                       
           >100                                                           
               40 50 60 >100                                              
                            >100                                          
                                >100                                      
                                    >100                                  
Pencil Hardness                                                           
           HB  2B HB 3B HB  2B  F   HB                                    
Impact Resistance                                                         
Direct, in. lbs.                                                          
           <5  10 25 10 50  <5  <5  <5                                    
Reverse, in. lbs.                                                         
           25  25 75 50 50  50  50  50                                    
__________________________________________________________________________
 *An acrylatefunctional, aliphatic urethane acrylate solution. It contains
 75% of a urethane acrylate oligomer and 25% 1,6hexanediol diacrylate. It 
 is sold by Cargill Inc.                                                  
 **A benzoin ether photosensitizer that yields free radicals when exposed 
 to ultraviolet light radiation. It is sold by Stauffer Chemical Company.
Thus, addition of the products of this invention to other acrylates and mixtures of acrylates can improve the impact resistance and improve or not alter the hardness of the starting urethane acrylate. In contrast, addition of M-100 causes a decrease in coating hardness and less of an improvement in impact resistance. It is worth pointing out that it is necessary to add a reactive diluent, such as the products of this invention, to the urethane acrylate to decrease viscosity and improve coating application characteristics. As supplied, the urethane acrylate has a viscosity of 19,500 cp at 20° C. and 3,800 cp at 37.8° C. (manufacturer's specification).
EXAMPLE 86
This example describes the preparation of a carboxyl-terminated caprolactone acrylate wherein only 90 mole or equivalent percent of the anhydride is used. The example is not meant to limit the amount of anhydride that can be used in the practice of the invention.
To a 500 ml. glass reaction flask, 44.1 grams (0.45 equivalent) of maleic anhydride and 172.0 grams (0.50 equivalent) of M-100 caprolactone acrylate were added. The reaction flask was equipped with a stirrer, a thermometer, an air inlet and an air outlet. The reactants were heated to 90° C. and held there for two hours. After this time period the reactants were cooled to room temperature and stored for future use. Analysis indicated that the residue product had a Gardner Color of 1.0 and a viscosity of 374 cp at 25° C.
Ten grams of the above product were combined with 0.5 g of Irgacure 184 photoinitiator and 0.04 g of L-7604 surfactant. They were well mixed and then cast onto Bonderite steel panels with a #20 wire-wound rod. The liquid coating was cured by passing it twice under a 300 watt/inch Fusion Systems ultraviolet light source at 10 feet per mixture. Analysis indicated that the coating had a rating of 30 acetone double rubs, <6B pencil hardness, 100% crosshatch adhesion, a direct impact resistance of 150 in. lbs., and a reverse impact resistance of 125 in. lbs.
EXAMPLE 87
An epsilon-methyl-epsilon-caprolactone adduct of 2-hydroxyethylacrylate was prepared by placing 128 grams of epsilon-methyl-epsilon caprolactone in a 250 cc, four-necked glass reaction flask equipped with a stirrer, thermometer, an air inlet and an air outlet. This compound was heated to 130° C. and 58 grams of 2-hydroxyethylacrylate, 0.009 gram of stannous octanoate, and 0.06 gram of the monomethylether of hydroquinone were slowly added. After the addition, the temperature dropped to 110° C. The mixture was then heated to 130° C. and held at this temperature for 14 hours. During this reaction time, an air sparge was maintained. After the reaction time had elapsed, the product, an epsilon-methyl-epsilon-caprolactone acrylate, was cooled to room temperature and stored.
Seventy-four and four-tenths grams of the lactone acrylate prepared above and 18.62 grams of maleic anhydride were placed in a four-neck, 250 cc glass reaction flask and heated to 90° C. An air sparge was used during the reaction. The temperature was maintained at 90° C. for two hours, after which time the product, an anhydride-capped methyl-caprolactone acrylate, was cooled to room temperature and stored. To 4.78 grams of this product, 0.20 gram of Irgacure 184 photoinitiator and 0.025 gram of L-5410 surfactant were added. These compounds were well mixed and then drawn down on Bonderite 37 steel panels with a #20 wire-wound rod. They were cured by exposing them five times to a Fusion Systems 300 watt/inch light source at 10 feet per minute. The cured coatings had the following characteristics: 30 acetone double rubs, 6B pencil hardness, 100% crosshatch adhesion, and 320 in. lbs direct and reverse Gardner impact resistance.
EXAMPLE 88
A maleic anhydride-capped caprolactone acrylate was prepared from 172.0 grams of M-100 caprolactone acrylate and 49.0 grams of maleic anhydride by using the same equipment, reaction conditions, and reaction times as were used in Example 86. The final product had a viscosity of 402 cp at 25° C. The product was stored for later usage.
EXAMPLES 89 to 97
These examples further demonstrate that the compounds of this invention can be combined with urethane acrylates to improve the hardness of coatings. In addition, the examples point out that the maleic anhydride-terminated caprolactone acrylates give improvements over those obtained when M-100, a caprolactone acrylate, is added to the formulation at the same level.
The ingredients listed in Table XIII were placed in amber colored glass bottles, mixed, and coated onto Bonderite 37 steel panels with a #20 wire-wound rod. The liquid coatings were then cured with a 300 watt per inch Fusion systems ultraviolet light source at 10 feet per minute.
                                  TABLE XIII                              
__________________________________________________________________________
           Example                                                        
           89  90  91  92  93  94  95  96  97                             
__________________________________________________________________________
Ingredients                                                               
Example 86 Product                                                        
           2.67                                                           
               --  --  1.67                                               
                           --  --  3.50                                   
                                       --  --                             
Example 88 Product                                                        
           --  2.67                                                       
                   --  --  1.67                                           
                               --  --  3.50                               
                                           --                             
M-100      --  --  2.67                                                   
                       --  --  1.67                                       
                                   --  --  3.50                           
Cargill XP-1512                                                           
           7.00                                                           
               7.00                                                       
                   7.00                                                   
                       7.00                                               
                           7.00                                           
                               7.00                                       
                                   4.00                                   
                                       4.00                               
                                           4.00                           
TMP-Triacrylate                                                           
           --  --  --  2.00                                               
                           2.00                                           
                               2.00                                       
                                   2.17                                   
                                       2.17                               
                                           2.17                           
Irgacure 184                                                              
           0.30                                                           
               0.30                                                       
                   0.30                                                   
                       0.30                                               
                           0.30                                           
                               0.30                                       
                                   0.30                                   
                                       0.30                               
                                           0.30                           
L-5410     0.05                                                           
               0.05                                                       
                   0.05                                                   
                       0.05                                               
                           0.05                                           
                               0.05                                       
                                   0.05                                   
                                       0.05                               
                                           0.05                           
Properties After Cure                                                     
Double Acetone Rubs                                                       
           >100                                                           
               >100                                                       
                   >100                                                   
                       >100                                               
                           >100                                           
                               >100                                       
                                   >100                                   
                                       >100                               
                                           >100                           
Pencil Hardness                                                           
           3H  3H  H   3H  4H  F   2H  2H  H                              
Impact Resistance                                                         
Direct, in. lbs.                                                          
           150 75  125 25  25  50  25  25  25                             
Reverse, in. lbs.                                                         
           125 75  <75 <10 <10 <10 <5  <5  5                              
__________________________________________________________________________
EXAMPLE 98
Eta-caprlolactone (21.0 grams), 2-hydroxyethylacrylate (8.53 grams), stannous octanoate (0.003 gram), and the monomethylether of hydroquinone (0.02 gram) were placed in a 250 cc glass, four-necked reaction flask equipped with a stirrer, thermometer, an air inlet and an air outlet. These ingredients were heated at 130° C. for 8 hours while an air sparge was maintained. The resulting lactone acrylate was cooled to room temperature and stored. The resulting product solidified into a crystalline mass. This product will be referred to as Example 98 Control Product in the following.
Twenty grams of Example 98 Control Product and 4.9 grams of maleic anhydride were placed in the reaction flask described in the previous paragraph and heated to 90° C. The ingredients were maintained at this temperature for two hours while maintaining an air sparge. The product was then cooled to room temperature and stored for further use. This product will be referred to as Example 98 Product in the following experimentation.
The ingredients shown in Table XIV were placed in amber colored glass bottles, well mixed, and coated onto Bonderite 37 steel panels with a #20 wire-wound rod. The liquid films were cured in a 300 watt per inch Fusion Systems ultraviolet light source at 10 feet per minute.
              TABLE XIV                                                   
______________________________________                                    
                 Run A   Run B                                            
______________________________________                                    
Ingredients                                                               
Example 98 Control Product                                                
                   4.78      --                                           
Example 98 Product --        4.78                                         
Irgacure 184       0.20      0.20                                         
L-5410             0.025     0.025                                        
Properties After Cure                                                     
Double Acetone Rubs                                                       
                   22        20                                           
Pencil Hardness    <6B       5B                                           
% Crosshatch Adhesion                                                     
                   100       100                                          
Gardner Impact                                                            
Direct, in. lbs.   150       275                                          
Reverse, in. lbs.  50        200                                          
______________________________________
These data demonstrate that the products of this invention have improved physical characteristics over those of the starting lactone acrylate which is an eta-caprololactone acrylate in this example.
EXAMPLE 99
The following ingredients were placed in a 250 cc glass, four-necked reaction flask that was equipped with a stirrer, thermometer, and an air inlet and outlet.
______________________________________                                    
Epsilon-methyl-epsilon-caprolactone                                       
                         128.00  g                                        
2-Hydroxyethylacrylate   29.00   g                                        
Stannous Octanoate       0.15    g                                        
Monomethylether of hydroquinone                                           
                         0.05    g                                        
______________________________________
These ingredients were heated to 130° C. and reacted at this temperature for 38 hours. An air sparge was maintained throughout the reaction period. The reactant product was then cooled to room temperature and stored for future use. It had a viscosity of 218 cp at 25° C.
EXAMPLE 100
94.20 grams of the Example 99 product, a methyl-caprolactone acrylate, and 13.23 grams of maleic anhydride were placed in a 250 cc, glass, four-necked reaction flask equipped with a stirrer, thermometer, an air inlet and an air outlet. These ingredients were heated to 90° C. and held at this temperature for two hours. After this time the carboxyl-terminated caprolactone acrylate was cooled to room temperature and stored for further use. It had a viscosity of 434 cp at 25° C.
EXAMPLES 101-104
The ingredients given in Table XV were placed in amber colored glass bottles, well mixed, and coated onto Bonderite 37 steel panels with a #20 wire-wound rod. They were then cured with three passes under a 300 watt per inch Fusion Systems ultraviolet light source at 10 fpm.
              TABLE XV                                                    
______________________________________                                    
            Example                                                       
            101     102     103      104                                  
______________________________________                                    
Ingredients                                                               
Example 99 Product                                                        
              5.0       2.5     --     --                                 
Example 100 Product                                                       
              --        --      5.0    2.5                                
TMP-triacrylate                                                           
              --        2.5     --     2.5                                
Irgacure 184  0.15      0.15    0.15   0.15                               
L-5410         0.025     0.025   0.025  0.025                             
Cured Properties                                                          
Double Acetone Rubs                                                       
              8         >100    20     >100                               
Pencil Hardness                                                           
              *         HB      <6B    2H                                 
% Crosshatch Adhesion                                                     
              *         95      100    100                                
Gardner Impact                                                            
Direct, in. lbs.                                                          
              *         10      320    15                                 
Reverse, in. lbs.                                                         
              *         <5      320    <5                                 
______________________________________                                    
 *Cured coating was somewhat tacky and full testing was not carried out.  
 The glass transition temperature of the amorphous coating was below room 
 temperature and therefore coating would not cure to a tackfree coating.
The above results further demonstrate that the cured products of this invention have improved hardness and impact resistance over those of the corresponding lactone acrylate.
EXAMPLE 105
This example describes the preparation of a copolymeric, epsilon-methyl-epsilon-caprolactone/epsilon-caprolactone, caprolactone acrylate and the corresponding anhydride-capped adduct of said caprolactone acrylate.
The following ingredients were placed in a 250 cc glass, four-necked reaction flask that was equipped with a stirrer, thermometer, an air inlet and an air outlet.
______________________________________                                    
Epsilon-methyl-epsilon-caprolactone                                       
                       38.4     g                                         
Epsilon-caprolactone   79.8     g                                         
______________________________________
These ingredients were heated to about 50°-60° C. and, while agitating and sparging with air, the following ingredients were added.
______________________________________                                    
2-Hydroxyethyl acrylate                                                   
                      58.00     g                                         
Dibutyl-tin-dilaurate 0.05      g                                         
Stannous octanoate    0.05      g                                         
Monomethylether of hydroquinone                                           
                      0.06      g                                         
______________________________________
The ingredients were heated to 130° C. and held at this temperature for 11 hours while stirring and sparging with air. After this time, the reaction product, Product P, was cooled to room temperature and stored for later use.
Eighty grams of Product P and 21.1 grams of maleic anhydride were placed in the above described reactor and heated to 90° C. The reactants were held at this temperature for two hours and the resulting anhydride-capped caprolactone acrylate was cooled to room temperature and recovered as a residue product.
EXAMPLE 106
This example illustrates the preparation of the acetate of TONE Monomer M-100.
One hundred grams of M-100 caprolactone acrylate were placed in a 250-milliliter, four-neck glass reaction flask that was equipped with a thermometer, stirrer, air inlet/outlet, and 26.7 grams of acetic anhydride were placed in a glass feeding tank that was attached to the reaction flask. About one-fourth of the acetic anhydride was added to the M-100. Since no exotherm occurred, a second one-fourth of the acetic anhydride was added. Since no exotherm occurred, the system was heated to 50°-60° C. and held at this temperature while the remaining acetic anhydride was added. The reactants were then held at 50°-60° C. for two hours, after which time the temperature was raised to 100° C. The resulting product was allowed to cool to room temperature and then vacuum stripped for 45 minutes. This product was then washed four times with distilled water, dried and stored. The product had a viscosity of 70 cp at 25° C.
EXAMPLES 107-109
The ingredients listed in Table XVI were placed in amber-colored glass bottles, mixed well, and coated onto Bonderite #37 steel panels with a #20 wire-wound rod. They were then cured by exposure to a 300 watt/inch, Fusion Systems ultraviolet light source.
              TABLE XVI                                                   
______________________________________                                    
               Example                                                    
               107    108      109                                        
______________________________________                                    
Ingredients                                                               
Product of Example 106                                                    
                 9.65 g   3.00 g   2.00 g                                 
TMP triacrylate  --       7.00 g   7.00 g                                 
Irgacure 184     0.40 g   0.40 g   0.40 g                                 
L-7604           0.04 g   0.04 g   0.04 g                                 
EX. 889 Product  --       --       1.00 g                                 
Properties After Cure                                                     
Double Acetone Rubs                                                       
                 15       100*     100*                                   
Pencil Hardness  6B       3H       3H                                     
% Crosshatch Adhesion                                                     
                 10       100      100                                    
Gardner Impact, In. lbs.                                                  
Direct           320*     10       10                                     
Reverse          320*     5**      5**                                    
______________________________________                                    
 *Property was greater than value indicated, but this is the highest value
 that was measured.                                                       
 **Property was less than the value indicated, but this is the lowest valu
 that could be measured.
Although the invention has been described in its preferred forms with a certain degree of particularity, it is understood that the present disclosure has been made only by way of example and that numerous changes can be made without departing from the spirit and scope of the invention.

Claims (12)

We claim:
1. A polymerizable monomer having the structure:
CH.sub.2 ═CRCO.sub.2 R'--O[COR"--O].sub.m COR'""--[COOH].sub.z
wherein R is H, methyl or ethyl, R' is an alkylene radical having 2 to about 12 carbons, R" is an alkylene radical having about 1 to about 10 carbons, R'" is a radical having 2 to about 20 carbons, m is an integer having a value of 1 to about 20, and z is an integer having a value of 1 to about 4.
2. Monomer claimed in claim 1 wherein R is H, R' is ethylene, R" is pentylene and R'" is --CH═CH--, and z is 1.
3. Monomer claimed in claim 1 wherein R is CH3 --, R' is ethylene, R" is pentylene, and R'" is --CH═CH--, and z is 1.
4. Monomer claimed in claim 1 wherein R'" is phenylene.
5. Monomer claimed in claim 1 wherein R is H, R' is ethylene, R" is 1-methyl-pentylene, and R'" is --CH═CH--, and z is 1.
6. Monomer claimed in claim 1 wherein R is H, R' is ethylene, R" is a mixture of pentylene and 1-methyl-pentylene, R'" is --CH═CH--, and z is 1.
7. Monomer claimed in claim 1 wherein R is H, R' is ethylene, R" is octylene, and R'" is --CH═CH--, and z is 1.
8. Monomer claimed in claim 1 wherein R'" is cyclohexylene.
9. Monomer claimed in claim 1 wherein R'" is methyl tetrahydrophenylene.
10. Monomer claimed in claim 1 wherein R'" is --CH2 C(═CH2)--.
11. Monomer claimed in claim 1 wherein m is 1 to about 10, and z is 1 to 2.
12. Monomer claimed in claim 1, wherein m is 1 to about 10.
US06/831,777 1986-02-20 1986-02-20 Carboxyl-terminated lactone acrylates Expired - Lifetime US4786749A (en)

Priority Applications (16)

Application Number Priority Date Filing Date Title
US06/831,777 US4786749A (en) 1986-02-20 1986-02-20 Carboxyl-terminated lactone acrylates
CA000530088A CA1318326C (en) 1986-02-20 1987-02-19 Carboxyl-terminated lactone acrylates
AU69110/87A AU6911087A (en) 1986-02-20 1987-02-20 Carboxylate cadded lactone acrylates
AT87102441T ATE103583T1 (en) 1986-02-20 1987-02-20 LACTONE ACRYLATE WITH CARBOXYL AS END GROUP.
DK086987A DK86987A (en) 1986-02-20 1987-02-20 CARBOXYL TERMINATED LACTON ACRYLATES, THEIR PREPARATION AND USE
BR8700817A BR8700817A (en) 1986-02-20 1987-02-20 LACTONE ACRYLATES FINISHED IN CARBOXYL
NO870685A NO870685L (en) 1986-02-20 1987-02-20 CARBOXYL-TERMINATED LACTON ACRYLATES.
EP87102441A EP0235704B1 (en) 1986-02-20 1987-02-20 Carboxyl-terminated lactone acrylates
DE3789464T DE3789464T2 (en) 1986-02-20 1987-02-20 Lactone acrylate with carboxyl as the end group.
JP62036003A JP2527952B2 (en) 1986-02-20 1987-02-20 Carboxyl-terminated lactone acrylate
KR870001421A KR870007961A (en) 1986-02-20 1987-02-20 Carboxyl-terminated Lactone Acrylate
SG105594A SG105594G (en) 1986-02-20 1994-07-30 Carboxyl-terminated lactone acrylates
JP6271810A JP2811542B2 (en) 1986-02-20 1994-10-12 Composition containing carboxyl-terminated lactone acrylate monomer
JP6271811A JP2617429B2 (en) 1986-02-20 1994-10-12 Carboxyl-terminated lactone acrylate
JP8221892A JP2893656B2 (en) 1986-02-20 1996-08-06 Composition containing carboxyl-terminated lactone acrylate monomer
JP10032393A JP2954917B2 (en) 1986-02-20 1998-01-30 Composition containing carboxyl-terminated lactone acrylate monomer

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AU (1) AU6911087A (en)
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CA (1) CA1318326C (en)
DE (1) DE3789464T2 (en)
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Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5506320A (en) * 1987-05-07 1996-04-09 The B. F. Goodrich Company Reactive modifier of elastomeric comb copolymer for thermosetting resins and process for making the same
US6045973A (en) * 1998-12-11 2000-04-04 Morton International, Inc. Photoimageable compositions having improved chemical resistance and stripping ability
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US20030175615A1 (en) * 2000-01-25 2003-09-18 Hiroto Miyake Photocurable resin composition
US20050192374A1 (en) * 2004-01-29 2005-09-01 Weitao Jia Dental resin composition, method of manufacture, and method of use thereof
US9428316B2 (en) 2010-08-19 2016-08-30 Toyo Seikan Group Holdings, Ltd. Resin for oxygen-absorbing adhesive and oxygen-absorbing adhesive
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US20200203763A1 (en) * 2018-12-20 2020-06-25 Robert Bosch Gmbh High-voltage stable copolymer for constituting a polymer electrolyte for a lithium or sodium cell

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Citations (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US29131A (en) * 1860-07-10 Improvement in harvesters of corn and sugar-cane
US30234A (en) * 1860-10-02 Planing valve-seats of steam-engines
US3367992A (en) * 1964-06-05 1968-02-06 Dow Chemical Co 2-hydroxyalkyl acrylate and methacrylate dicarboxylic acid partial esters and the oxyalkylated derivatives thereof
US3451980A (en) * 1966-03-09 1969-06-24 Princeton Chemical Res Inc Anaerobic adhesive
US3455802A (en) * 1966-03-02 1969-07-15 Ppg Industries Inc Highly radiation-sensitive telomerized polyesters
US3655631A (en) * 1968-11-20 1972-04-11 Laporte Industries Ltd Polymerisation process
US3760034A (en) * 1971-01-26 1973-09-18 Union Carbide Corp Graft copolymers of lactone polyesters
US3816566A (en) * 1971-01-26 1974-06-11 Union Carbide Corp Graft copolymer of lactone polyesters and blends thereof with pvc
US3864434A (en) * 1972-07-19 1975-02-04 Union Carbide Corp Graft copolymers of Lactone Polyesters and Blends with Polyvinyl Chloride
US3884994A (en) * 1972-07-19 1975-05-20 Union Carbide Corp Graft copolymers of lactone polyesters
US3892714A (en) * 1971-12-09 1975-07-01 Laporte Industries Ltd Hydroxy copolymer reacted with a lactone and polyisocyanate crosslinked
US4000218A (en) * 1973-12-03 1976-12-28 Union Carbide Corporation Process for preparing particulate polyurethane polymers and the polymers derived therefrom
USRE29131E (en) 1970-09-02 1977-02-01 Union Carbide Corporation Radiation-curable acrylate-capped polycaprolactone compositions
US4034017A (en) * 1973-08-29 1977-07-05 Ppg Industries, Inc. Composition useful in making extensible films
US4082816A (en) * 1972-09-18 1978-04-04 Cook Paint And Varnish Company Caprolactone polymers from unsaturated monomers
US4171423A (en) * 1977-09-29 1979-10-16 Union Carbide Corporation Derivatives of ester diol alkoxylates and compositions thereof
US4188477A (en) * 1977-09-29 1980-02-12 Union Carbide Corporation Isocyanate derivatives of ester diol alkoxylates and compositions thereof
US4188472A (en) * 1978-10-06 1980-02-12 Ppg Industries, Inc. Curable lactone derived resins
US4192789A (en) * 1977-09-29 1980-03-11 Union Carbide Corporation Blends of acrylic latexes and derivatives of ester diol alkoxylates
USRE30234E (en) 1971-12-09 1980-03-18 Laporte Industries, Limited Polymeric compositions
US4195160A (en) * 1977-09-29 1980-03-25 Union Carbide Corporation Epoxide derivatives of ester diol alkoxylates and compositions thereof
US4281172A (en) * 1980-03-21 1981-07-28 Union Carbide Corporation Acrylyl esters of polyester-polyether copolymers
US4317760A (en) * 1979-07-31 1982-03-02 Dainippon Ink And Chemicals, Inc. Halogen-containing resin composition
US4340497A (en) * 1980-03-21 1982-07-20 Union Carbide Corporation (N-Substituted carbamoyloxy) alkanoyloxyalkyl acrylate esters
US4439599A (en) * 1981-10-02 1984-03-27 Daicel Chemical Industries, Ltd. Polyurethane having excellent elastic recovery and elastic filament of the same
US4504635A (en) * 1982-11-02 1985-03-12 Union Carbide Corporation Process for the preparation of polymeric compositions
US4525258A (en) * 1982-02-05 1985-06-25 Daicel Chemical Industries, Ltd. Radiation-curable resin composition
GB2160534A (en) * 1984-06-11 1985-12-24 Interox Chemicals Ltd Cross-linkable polymeric coating compositions

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS4873196A (en) * 1971-12-28 1973-10-02
EP0099675B1 (en) * 1982-07-03 1985-09-04 Smith and Nephew Associated Companies p.l.c. Polymerisable compounds, their preparation and adhesive surgical or medical dressing comprising these compounds
JPS62161742A (en) * 1986-01-08 1987-07-17 Nippon Paint Co Ltd Terminal carboxyl group-containing reactive acrylic monomer and production thereof
US4786749A (en) * 1986-02-20 1988-11-22 Union Carbide Corporation Carboxyl-terminated lactone acrylates

Patent Citations (29)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US30234A (en) * 1860-10-02 Planing valve-seats of steam-engines
US29131A (en) * 1860-07-10 Improvement in harvesters of corn and sugar-cane
US3367992A (en) * 1964-06-05 1968-02-06 Dow Chemical Co 2-hydroxyalkyl acrylate and methacrylate dicarboxylic acid partial esters and the oxyalkylated derivatives thereof
US3455802A (en) * 1966-03-02 1969-07-15 Ppg Industries Inc Highly radiation-sensitive telomerized polyesters
US3451980A (en) * 1966-03-09 1969-06-24 Princeton Chemical Res Inc Anaerobic adhesive
US3655631A (en) * 1968-11-20 1972-04-11 Laporte Industries Ltd Polymerisation process
USRE29131E (en) 1970-09-02 1977-02-01 Union Carbide Corporation Radiation-curable acrylate-capped polycaprolactone compositions
US3760034A (en) * 1971-01-26 1973-09-18 Union Carbide Corp Graft copolymers of lactone polyesters
US3816566A (en) * 1971-01-26 1974-06-11 Union Carbide Corp Graft copolymer of lactone polyesters and blends thereof with pvc
US3892714A (en) * 1971-12-09 1975-07-01 Laporte Industries Ltd Hydroxy copolymer reacted with a lactone and polyisocyanate crosslinked
USRE30234E (en) 1971-12-09 1980-03-18 Laporte Industries, Limited Polymeric compositions
US3864434A (en) * 1972-07-19 1975-02-04 Union Carbide Corp Graft copolymers of Lactone Polyesters and Blends with Polyvinyl Chloride
US3884994A (en) * 1972-07-19 1975-05-20 Union Carbide Corp Graft copolymers of lactone polyesters
US4082816A (en) * 1972-09-18 1978-04-04 Cook Paint And Varnish Company Caprolactone polymers from unsaturated monomers
US4034017A (en) * 1973-08-29 1977-07-05 Ppg Industries, Inc. Composition useful in making extensible films
US4000218A (en) * 1973-12-03 1976-12-28 Union Carbide Corporation Process for preparing particulate polyurethane polymers and the polymers derived therefrom
US4195160A (en) * 1977-09-29 1980-03-25 Union Carbide Corporation Epoxide derivatives of ester diol alkoxylates and compositions thereof
US4171423A (en) * 1977-09-29 1979-10-16 Union Carbide Corporation Derivatives of ester diol alkoxylates and compositions thereof
US4188477A (en) * 1977-09-29 1980-02-12 Union Carbide Corporation Isocyanate derivatives of ester diol alkoxylates and compositions thereof
US4192789A (en) * 1977-09-29 1980-03-11 Union Carbide Corporation Blends of acrylic latexes and derivatives of ester diol alkoxylates
US4188472A (en) * 1978-10-06 1980-02-12 Ppg Industries, Inc. Curable lactone derived resins
US4317760A (en) * 1979-07-31 1982-03-02 Dainippon Ink And Chemicals, Inc. Halogen-containing resin composition
US4421885A (en) * 1979-07-31 1983-12-20 Dainippon Ink And Chemicals, Inc. Halogen-containing resin composition containing ester plasticizer
US4281172A (en) * 1980-03-21 1981-07-28 Union Carbide Corporation Acrylyl esters of polyester-polyether copolymers
US4340497A (en) * 1980-03-21 1982-07-20 Union Carbide Corporation (N-Substituted carbamoyloxy) alkanoyloxyalkyl acrylate esters
US4439599A (en) * 1981-10-02 1984-03-27 Daicel Chemical Industries, Ltd. Polyurethane having excellent elastic recovery and elastic filament of the same
US4525258A (en) * 1982-02-05 1985-06-25 Daicel Chemical Industries, Ltd. Radiation-curable resin composition
US4504635A (en) * 1982-11-02 1985-03-12 Union Carbide Corporation Process for the preparation of polymeric compositions
GB2160534A (en) * 1984-06-11 1985-12-24 Interox Chemicals Ltd Cross-linkable polymeric coating compositions

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
Nippon Kayaku Chemical Abstracts, vol. 102:15124s, 1983. *
Nippon Kayaku Derwent Abstracts 84 033042/06, 1984. *
Nippon Kayaku--Chemical Abstracts, vol. 102:15124s, 1983.
Nippon Kayaku--Derwent Abstracts 84-033042/06, 1984.
Research Disclosure, No. 265, May 1986, Disclosure No. 26564, pp. 296 297. *
Research Disclosure, No. 265, May 1986, Disclosure No. 26564, pp. 296-297.

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5506320A (en) * 1987-05-07 1996-04-09 The B. F. Goodrich Company Reactive modifier of elastomeric comb copolymer for thermosetting resins and process for making the same
US6045973A (en) * 1998-12-11 2000-04-04 Morton International, Inc. Photoimageable compositions having improved chemical resistance and stripping ability
SG79295A1 (en) * 1998-12-11 2001-03-20 Shipley Co Llc Photoimageable compositions having improved chemical resistance and stripping ability
US20030175615A1 (en) * 2000-01-25 2003-09-18 Hiroto Miyake Photocurable resin composition
US20050192374A1 (en) * 2004-01-29 2005-09-01 Weitao Jia Dental resin composition, method of manufacture, and method of use thereof
US7700667B2 (en) * 2004-01-29 2010-04-20 Pentron Clinical Technologies, Llc Dental resin composition, method of manufacture, and method of use thereof
US9428316B2 (en) 2010-08-19 2016-08-30 Toyo Seikan Group Holdings, Ltd. Resin for oxygen-absorbing adhesive and oxygen-absorbing adhesive
CN107960085A (en) * 2016-03-31 2018-04-24 哈利玛化成株式会社 Metal particle dispersion liquid and cured film
CN107960085B (en) * 2016-03-31 2019-03-26 哈利玛化成株式会社 Metal particle dispersion liquid and cured film
US20200203763A1 (en) * 2018-12-20 2020-06-25 Robert Bosch Gmbh High-voltage stable copolymer for constituting a polymer electrolyte for a lithium or sodium cell
US11462768B2 (en) * 2018-12-20 2022-10-04 Robert Bosch Gmbh High-voltage stable copolymer for constituting a polymer electrolyte for a lithium or sodium cell

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NO870685L (en) 1987-08-21
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CA1318326C (en) 1993-05-25
JP2527952B2 (en) 1996-08-28
JPH09118724A (en) 1997-05-06
EP0235704A2 (en) 1987-09-09
DK86987D0 (en) 1987-02-20
DE3789464D1 (en) 1994-05-05
JPH10310723A (en) 1998-11-24
EP0235704A3 (en) 1989-05-17
DE3789464T2 (en) 1994-07-28
NO870685D0 (en) 1987-02-20
DK86987A (en) 1987-08-21
JP2954917B2 (en) 1999-09-27
KR870007961A (en) 1987-09-23
BR8700817A (en) 1987-12-15
JP2893656B2 (en) 1999-05-24
ATE103583T1 (en) 1994-04-15
JPH07258350A (en) 1995-10-09
JPH07258162A (en) 1995-10-09
JPS62265249A (en) 1987-11-18
JP2811542B2 (en) 1998-10-15
EP0235704B1 (en) 1994-03-30

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